DE60113613T2 - Toner, image forming process and process cartridge - Google Patents

Description

BACKGROUND THE INVENTION

Field of the invention

These This invention relates to a toner used in imaging Methods such as electrophotography, electrostatic recording, electrostatic printing and ink jet recording, and relates also to an image-forming process and to a process cartridge, which makes use of the toner.

related State of the art

A Number of methods as disclosed in U.S. Patent No. 2,297,691, Japanese Patent Publication Nos. 42-23910 and 43-24748 are known as methods for electrophotography. In general, recorded images are obtained by generating an electrostatic latent image on a photosensitive Element by various means using a photoconductive material, subsequently developing the latent image through use a toner to form a toner image, and transferring the toner image a transmission medium like paper, followed by fixing by the action of heat, pressure, Heat and Pressure, or solvent vapor.

There in recent years copiers and printers have been made to have multiple functions to take pictures in a higher one picture quality Record and increase the process speed it is for The toners have also become necessary to possess a much stricter performance. Accordingly, become Toner made smaller in particle diameter, and it is necessary that they have a particle size distribution which is sharp enough that no coarse particles and less ultrafine powder is included.

toner to make it have a smaller particle diameter, can the resolution and the sharpness Improving images, however, brings with it many problems yourself.

On the one hand does that Create a toner with a small particle diameter to one larger specific surface of the toner and thus to a broad distribution of its charge quantity, to cause fog on non-image areas when the toner on the Development participates. Likewise, the chargeability of the toners tends more to be influenced by the environment. To a lower occurrence to accomplish this veiling is also attempted Toner to have a sharp particle size distribution. However, this can be the cause of an increase in costs due, for example, to a low yield in the production the toner.

Furthermore The dispersibility of other internal additives tends to be higher in the binder resin to more strongly influence the performance of the toner, though Toner can be made to have a small particle diameter have.

Around to cope with such problems, become ordinary Charge control agents added to toners to give the toners the desired to convey triboelectric charges.

nowadays shut down the charge control agents based on the present technical Are known, metal complexes of monoazo dyes, metal complexes of hydroxycarboxylic acids, dicarboxylic acids or aromatic diols and resins containing acidic components, known as negative triboelectric charge control agents are. As positive triboelectric charge control agents are known in the art nigrosine dyes, azine dyes, Triphenylmethane dyes, quaternary Ammonium salts and polymers with a quaternary ammonium salt in the side chain. However, most of these charge control agents are dyes and are often unusable in colored toners.

Additional wise some charge control agents have disadvantages that it is difficult To compensate for image density and fog, that it is difficult is, sufficient image density in a high humidity environment to achieve that they have poor dispersibility in resins possess, and they can adversely affect the Storage stability, the fixing property and anti-offset properties.

Under the aspect of triboelectric charge control and safety In recent years, studies have been conducted on charge control resins performed. Japanese Patent Application Laid-Open No. 63-184762 discloses a process in which a polymer of a styrene monomer used with 2-acrylamide-2-methylsulfonic acid becomes. Japanese Laid-Open Patent Application No. 3-161761 discloses a method in which the polymer of a styrene monomer with 2-acrylamide-2-methylsulfonic acid is used is used as a charge control agent with respect to a polyester resin. Japanese Laid-Open Patent Application No. 2000-56518 is disclosed a toner containing as a charge control agent a sulfonic acid group-containing acrylic or methacrylamide copolymer having a specific glass transition temperature. These methods can a superior one provide triboelectric chargeability, but you can not claim that they are satisfactory based on an environmental condition Change, Expiry of the time and condition of use, thus in an adequate manner must be handled when the toners are made to one have smaller particle diameter, especially in creating a higher one Picture quality, and also with respect to an improvement in transmission efficiency considering environmental issues, how later explained becomes.

In Transfer residual toner is present in the above photographic process on the photosensitive member after transferring the toner image has been from the surface of the photosensitive member on the transfer medium. To a continuous Copy quickly, This residual toner on the photosensitive element must be cleaned by cleaning be removed. The thus removed and collected residual toner is further into a container or collection container given within the main structure, and is then discarded or over recovered a circulation step.

Around with environmental issues Getting ready is an arrangement that's designed to be a recovery system to provide within the main structure required as one Waste toner-less system. However, to photocopiers and printers to have multiple functions, images in one higher picture quality record and a higher Owning process speed is quite a bit in the main setup great Recovery system required, resulting in large copy machines and printers leads. This is from the point of view of space saving in creating of devices small size not feasible. The same applies to a system in which the waste toner is kept in a container or a collection container which is provided inside the main body and for a system in which the photosensitive element and the part where the waste toner is collected in one unit.

Around so that in adequate To deal with it, it is necessary to improve the transmission efficiency, the is required when the toner image is transferred from the surface of the Photosensitive element on the transmission medium.

Japanese Patent Application Laid-Open No. 9-26672 discloses a method in which a toner prepared by pulverizing a transfer efficiency improver having an average particle diameter of 0.1 to 3 μm and a hydrophobic fine silica powder having a BET specific surface area of 50 to 300 m ² / g, so that the toner may have a low volume resistivity, and the transfer efficiency improver may form a thin film layer on the photosensitive member to improve the transfer efficiency. However, since the toner prepared by pulverization has a particle size distribution, it is difficult to provide a uniform effect on all the particles. Accordingly, it is necessary to provide further improvement.

When a means for improving transmission efficiency disclose Japanese Patent Application Laid-Open No. 3-84558, No. 3-229268, No. 4-1766 and No. 4-102862 Toner, manufactured by Methods such as spray granulation, Resolution, and polymerization so that toner particles have a shape can they close to balls. However, the preparation of such toner requires not only equipping on a large scale, but also causes a problem concerning the cleaning due to the toner particles which almost spherical were made.

As usual methods of producing toners, a binder resin is used as materials to make the toner adhere to the transfer media, a dye of various kinds to give a color to the toner, and a charge controlling agent for supplying electric charges to the toner particles to convey. In addition to such materials, in a one-part development, as disclosed in Japanese Patent Application Laid-Open No. 54-42141 and No. 55-18656, a magnetic material of various kinds is added to impart a transporting property to the toner itself. If necessary, other additives such as a release agent and fluidity will also be provided of the agent, and these are mixed in a dry process. Thereafter, the resulting mixture is melt-kneaded by means of a general-purpose kneading machine such as a roll mill or an extruder, followed by cooling for solidification, and then the kneaded product is crushed. The crushed product obtained is pulverized by means of a grinding machine of various kinds, such as a jet groover and a mechanical impact grinding machine. Thereafter, the obtained pulverized product is introduced into an air classifier of various kinds to perform a classification to obtain toner particles having particle diameters necessary as a toner, optionally followed by further external addition of a condenser or a lubricant, and mixing in a dry process to obtain toner. Also, in the case of two-component developers, the above toners are used after being mixed with various carriers.

In order to obtain fine toner particles as set forth above, an in 10 applied as a flowchart shown method.

The mashed Product for The toner is continuously or successively in a first classification device given. Classified coarse powder composed mainly of one Group of coarse particles larger than a prescribed one Particle size, will pulverized by a pulverizer, and becomes then circulated back to the first classifier.

Other finely pulverized product for Toner, which is mainly is composed of particles within the prescribed Particle size, and Particles smaller than the prescribed particle size will become sent to a second classifier, and is classified in a median powder, mainly is composed of a group of particles with the prescribed Particle size, and fine powder, mainly is composed of a group of particles that are smaller are considered the prescribed particle size. But if toner is be made to have a smaller particle diameter, can be an electrostatic aggregation between particles in great Dimensions occur. The toner particles, which originally should be sent to the second classifier, are circulated again into the first classifier, an overly pulverized one produce fine powder and ultrafine powder.

Various types of grinding machines are used as the pulverizer. To pulverize the crushed product composed mainly of binder resin, a jet groover, particularly a collision air milling machine, which makes use of jet streams, is used as in US Pat 13 shown, used.

In collision air milling machine using high pressure gas like nozzle streams makes a powder material is transported by nozzle streams and of a Outlet of an accelerator tube blasted to cause the powder material to collide against the colliding material surface of a collision member provided to the open one End of the outlet facing the accelerating tube, and the powder material is pulverized with the help of the impact of the collision.

In the collision air milling machine, which in 13 is shown, there is a collision element 164 in one of the outlet 163 an accelerating tube 162 facing manner, to which a Hochdruckgaszufuhrdüse 161 connected. With the help of high-pressure gas, which is supplied to the accelerating tube 162 , the powder material is in the accelerating tube 162 from a powder material supply port 165 Made to halfway with the accelerating tube 162 to communicate, sucked. The powder material is blasted along with the high pressure gas and caused to collide against the colliding surface 166 of the collision element 164 , and powdered with the help of the collision impact. The pulverized product is removed from a pulverization chamber 168 discharged via a discharge opening 167 for the powdered product.

Because However, the above Kollisionsluftmahlmaschine is constructed so that the powder material is blasted together with the high-pressure gas, and causing it to collide against the colliding surface of the Collision element collides, and is pulverized by means of Impact effect of the collision, the by pulverization thus obtained toner particles are amorphous and have a square shape.

Japanese Patent Application Laid-Open No. 2-87157 discloses a method in which toner particles prepared by pulverization are subjected to a mechanical impact (hybridizer) to modify the shape and surface properties of the particles to improve the transfer efficiency. However, this method requires the further provision of a post-treatment step for the pulverization, and thus can not be said to be a preferable method in view of the productivity of the toners, and also because the toner particle surfaces almost become a condition free of unevenness, which requires an improvement in development.

In Regarding the classifier were many types of Gas stream classifiers and methods proposed. Below are available one Classifier, which makes use of a rotating blade, and a classifier without a moving part. These include the classifier without moving part, a centrifugal classifier with stationary wall, and an inertial classifier. Such a classifier using an inertial force is disclosed in a Japanese patent publication No. 54-24745, and No. 55-6433, and Japanese Patent Application Laid-Open No. 63-101858.

In these gas stream classifiers, as in 8th As shown, a powder material is blasted into a classifying zone of a classifying chamber together with gas streams at a high speed from a feed nozzle having an opening at the classifying zone. In the classifying chamber, a centrifugal force separates from bent gas streams, which run along a Coanda block 145 flow, the powder material into coarse powder, median powder and fine powder, and edges 146 and 147 that have slender tips classify it into coarse powder, median powder and the fine powder.

In such a conventional classifier 57 For example, a finely pulverized material is introduced from a material supply nozzle. Powder particles which are inside the pyramidal tubes 148 and 149 Flow, have a tendency to flow with a screwing force, which acts directly parallel to the tube walls. In the material supply nozzle, however, the powder material roughly separates into an upper stream and a lower stream when it is introduced from the upper part. Light fine powder tends to be contained in the upper stream in a larger amount, and heavy coarse powder in the lower stream in a large amount where the corresponding particles flow independently of each other. Thus, depending on the part from which the powder material is introduced into the classifier, the respective flows may draw different loci, or the coarse powder disturbs the locus of the fine powder, which is accompanied with a limitation of improving the classification precision, and so on leads to reduce the precision when a powder material containing coarse particles of 20 microns or larger diameter in a large amount is classified.

in the Generally, it is necessary for many and different toners Own properties. Achieving such required Properties depends Naturally from the base materials to be used and also in many cases of the manufacturing process. In the classification step for toner is it for The classified particles require that they have a sharp particle size distribution have. It is also sought after, toner of good quality at low Cost, in good efficiency and in a sustainable way.

Around the picture quality in copiers and to improve printers, in addition toner in the particle diameter made smaller and it is required that they have a particle size distribution which is sharp enough that no coarse particles and contains little ultrafine powder. In general, if the Substance becomes finer, interparticle forces act to a greater extent. The same goes for resins and Toner, and particles become to each other to a greater extent clinging when they become finer in size.

Especially when trying to obtain a toner having a weight-average particle diameter of 10 μm or smaller, and to achieve a sharp particle size distribution, any conventional device and method causes a degradation of the Classification yield. Even if trying to use a toner with a weight average particle diameter of 8 microns or less, and a sharp Particle size distribution Achieve any conventional device and method in particular not only a reduction of the classification yield, but also tends to contain ultrafine powder in a big one To cause quantity.

Furthermore That's what the toners that are made of are a smaller one Having particle diameter is relatively important to the compatibility of each Materials that are contained in the toners, making a stricter restriction as before also regarding is imposed on the evolving property.

That is, the productivity of the toner itself involved is long awaited to provide a toner having a high developing performance which has been improved in the transfer the efficiency of efficiency with the intention of reducing the transfer residual toner on the photosensitive member left as a waste toner.

SUMMARY THE INVENTION

A The object of the present invention is to provide a toner with a transmission efficiency, which is high enough to leave less waste toner.

A Another object of the present invention is to provide a toner which can sustain good developing property, too with its small particle diameter.

Yet Another object of the present invention is to provide a toner provided by an environment of image reproduction is not affected, and can maintain a good developing Property also in a high temperature and high environment Moisture, and in an environment of normal temperature and low humidity.

A Another object of the present invention is to provide a toner which with ease in a high productivity through Pulverization can be made.

A Another object of the present invention is an image forming method which makes use of the above toner.

A Another object of the present invention is to provide a process cartridge to provide the above toner.

• a) die Beziehung zwischen Teilungsrate Z und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (2) genügt: Teilungsrate Z ≤ 5,3 × X (2)vorausgesetzt, dass die Teilungsrate Z dargestellt wird durch den folgenden Ausdruck (3): Z = (1 – B/A) × 100 (3)wobei A die Partikelkonzentration der gesamten gemessenen Partikel ist, wie gemessen gemäß einem Durchflusstyp-Partikelbildanalysator FPIA-1000, hergestellt von Toa Iyou Denshi K.K., und B die Partikelkonzentration der gemessenen Partikel von 3 μm oder größer im Kreis-entsprechenden Durchmesser ist; und in den Partikeln von 3 μm oder größer im Durchmesser des Toners, und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahl-basierenden kumulierten Wert Y der Partikel mit einer Kreisförmigkeit a von 0,950 oder höher, und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (4) genügt: Anzahl-basierender kumulierter Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,51 × X–0,645 (4)vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm–12,0 μm beträgt; oder
• b) die Beziehung zwischen der Teilungsrate Z und dem massgemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (5) genügt: Teilungsrate Z > 5,3 × X (5);und in den Partikeln von 3 μm oder größer im Durchmesser des Toners und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahl-basierenden kumulierten Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (6) genügt: Anzahl-basierender kumulierter Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,37 × X–0,545 (6)vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm–12,0 μm beträgt.

In order to solve the above problems, the present invention provides a toner having toner particles containing at least (I) a binder resin, (II) a dye, and (III) a sulfur-containing compound selected from the group consisting of sulfuric acid. containing polymer and a sulfur-containing copolymer, wherein
the toner has a weight average particle diameter of 5 μm to 12 μm; and
the toner among its particles, which are 3 μm or larger in diameter, has at least 90% by weight of particles having a circularity a of 0.900 or higher, as in the following expression (1): Circularity a = L 0 / L (1) where L ₀ represents the circumferential length of a circle having the same projected area as a particle image, and L represents the circumferential length of the particle image;
and where;

• a) the relationship between the division rate Z and the weight-average toner particle diameter X satisfies the following expression (2): Division rate Z ≤ 5.3 × X (2) provided that the division rate Z is represented by the following expression (3): Z = (1-B / A) × 100 (3) wherein A is the particle concentration of the total measured particles as measured according to a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and B is the particle concentration of the measured particles of 3 μm or larger in the circle-corresponding diameter; and in the particles of 3 μm or larger in diameter of the toner, and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of the particles having a circularity a of 0.950 or higher and the weight-average toner particle diameter X satisfies the following expression (4): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.51 × X -0.645 (4) provided that the weight average toner particle diameter X is from 5.0 μm-12.0 μm; or
• b) the relationship between the division rate Z and the mass average toner particle diameter X satisfies the following expression (5): Division rate Z> 5.3 × X (5); and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher and the weight-average toner particle diameter X dem the following expression (6) satisfies: Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.37 × X-0,545 (6) provided that the weight average toner particle diameter X is 5.0 μm-12.0 μm.

• a) die Beziehung zwischen Teilungsrate Z und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (2) genügt: Teilungsrate Z ≤ 5,3 × X (2)vorausgesetzt, dass die Teilungsrate Z dargestellt ist durch den folgenden Ausdruck (3): Z = (1 – B/A) × 100 (3)wobei A die Partikelkonzentration der gesamten gemessenen Partikel, wie gemessen mit einem Durchflusstyp-Partikelbildanalysator FPIA-1000, hergestellt von Toa Iyou Denshi K.K., und B die Partikelkonzentration der gemessenen Partikel von 3 μm oder größer im Kreis-entsprechenden Durchmesser ist; und in den Partikeln von 3 μm oder größer im Durchmesser des Toners und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahl-basierenden kumulierten Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher, und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (4) genügt: Anzahl-basierender kumulierter Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,51 × X–0,645 (4)vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm bis 12,0 μm beträgt; oder
• b) die Beziehung zwischen der Teilungsrate Z und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (5) genügt: Teilungsrate Z > 5,3 × X (5);und in den Partikeln von 3 μm oder größer im Durchmesser des Toners und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahl-basierenden kumulierten Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher, und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (6) genügt: Anzahl-basierender kumulierter Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,37 × X–0,545 (6)vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm bis 12,0 μm beträgt.

The present invention also provides an image forming method comprising;
Generating an electrostatic latent image on an electrostatic image bearing member;
Developing the electrostatic latent image with a toner held in a developing device to form a toner image;
Transferring the toner image formed in this manner to a transfer medium via, or not via, an intermediate transfer element;
Fixing the toner image carried on the transfer medium to the transfer medium by a heat and pressure fixing means;
in which;
the toner comprises toner particles containing at least (i) a binder resin, (ii) a dye, and (iii) a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, wherein;
the toner has a weight average particle diameter of 5 μm to 12 μm; and
the toner in its particles of 3 μm or larger in diameter has at least 90% by weight of particles with a circularity a of 0.900 or higher, as determined according to the following expression (1): Circularity a = L 0 / L (1) where L ₀ represents the circumferential length of a circle having the same projected area as a particle image, and L represents the circumferential length of the particle image;
and where

• a) the relationship between the division rate Z and the weight-average toner particle diameter X satisfies the following expression (2): Division rate Z ≤ 5.3 × X (2) provided that the division rate Z is represented by the following expression (3): Z = (1-B / A) × 100 (3) wherein A is the particle concentration of the total measured particles as measured by a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and B is the particle concentration of the measured particles of 3 μm or larger in the circle-corresponding diameter; and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher, and the weight-average toner particle diameter X satisfies the following expression (4): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.51 × X -0.645 (4) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm; or
• b) the relationship between the division rate Z and the weight average toner particle diameter X satisfies the following expression (5): Division rate Z> 5.3 × X (5); and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher, and the weight-average toner particle diameter X satisfies the following expression (6): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.37 × X -0.545 (6) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm.

• a) die Beziehung zwischen Teilungsrate Z und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (2) genügt: Teilungsrate Z ≤ 5,3 × X (2)vorausgesetzt, dass die Teilungsrate Z durch den folgenden Ausdruck (3) dargestellt ist: Z = (1 – B/A) × 100 (3)wobei A die Partikelkonzentration der gesamten gemessenen Partikel, wie gemessen mit einem Durchflusstyp- Partikelbildanalysator FPIA-1000, hergestellt von Toa Iyou Denshi K.K., und B die Partikelkonzentration der gemessenen Partikel von 3 μm oder größer im Kreis-entsprechenden Durchmesser ist; und in den Partikeln von 3 μm oder größer im Durchmesser des Toners und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahl-basierenden kumulierten Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher, und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (4) genügt: Anzahl-basierender kumulierter Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,51 × X–0,645 (4)vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm bis 12,0 μm ist; oder
• b) die Beziehung zwischen der Teilungsrate Z und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (5) genügt: Teilungsrate Z > 5,3 × X (5);und in den Partikeln von 3 μm oder größer im Durchmesser des Toners und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahl-basierenden kumulierten Wert Y der Partikel mit einer Kreisförmigkeit a von 0,950 oder höher, und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (6) genügt: Anzahl-basierender Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,37 × X–0,545 (6) vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm bis 12,0 μm beträgt.

The present invention also provides a process cartridge
an electrostatic image bearing member and developing means for developing an electrostatic latent image formed on the electrostatic image bearing member, with a toner;
wherein the electrostatic image bearing member and the developing means are supported in one unit to form the process cartridge, and the process cartridge is detachably mountable to the main body of an image forming apparatus;
in which
the toner comprises toner particles containing at least (i) a binder resin, (ii) a dye, and (iii) a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, wherein;
the toner has a weight average particle diameter of 5 μm to 12 μm; and
the toner in its particles of 3 μm or larger in diameter has at least 90% by weight of particles with a circularity a of 0.900 or higher, as determined according to the following expression (1): Circularity a = L 0 / L (1) where L ₀ represents the circumferential length of a circle having the same projected area as a particle image, and L represents the circumferential length of the particle image; and where;

• a) the relationship between the division rate Z and the weight-average toner particle diameter X satisfies the following expression (2): Division rate Z ≤ 5.3 × X (2) provided that the division rate Z is represented by the following expression (3): Z = (1-B / A) × 100 (3) wherein A is the particle concentration of the total measured particles as measured by a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and B is the particle concentration of the measured particles of 3 μm or larger in the circle-corresponding diameter; and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher, and the weight-average toner particle diameter X satisfies the following expression (4): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.51 × X -0.645 (4) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm; or
• b) the relationship between the division rate Z and the weight average toner particle diameter X satisfies the following expression (5): Division rate Z> 5.3 × X (5); and in the particles of 3 μm or larger in diameter of the toner and in the number-based circle Circularity a, the relationship between the number-based cumulative value Y of the particles having a circularity a of 0.950 or higher, and the weight-average toner particle diameter X satisfies the following expression (6): Number-based value Y of particles having a circularity a from 0.950 or higher ≥ e 5.37 × X -0.545 (6) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm.

SUMMARY THE DRAWINGS

1 Fig. 10 is a flow chart for describing a preferred method for producing the toner of the present invention.

2 Fig. 10 is a flowchart for describing another preferred method for producing the toner of the present invention.

3 Fig. 12 is a schematic view of an example of a system unit for carrying out a preferred method for producing the toner of the present invention.

4 Fig. 12 is a schematic view of another example of a system unit for carrying out a preferred method for producing the toner of the present invention.

5 Fig. 12 is a schematic cross-sectional view of an example of a mechanical grinding machine used in a pulverization step for producing toner particles.

6 is a schematic cross-sectional view taken along the line 6-6 in FIG 5 ,

7 FIG. 15 is a perspective view of a rotor shown in FIG 5 ,

8th Figure 11 is a schematic cross-sectional view of a multi-parted gas stream classifier used in the step of classifying toner particles.

9 FIG. 12 is a schematic cross-sectional view of a multi-division gas stream classifier, preferably used in the step of classifying toner particles. FIG.

10 Fig. 10 is a flow chart for describing a conventional method of producing toner particles.

11 Fig. 10 is a system diagram illustrating a conventional toner manufacturing process.

12 FIG. 12 is a schematic cross-sectional view of an example of a classifier conventionally used in a first classifier and a second classifier. FIG.

13 is a schematic cross-sectional view of a conventional collision air grinding machine.

14 Figure 3 is a graph of the particle size distribution of a median powder A-1.

15 Fig. 12 is a graph of the circularity distribution of the median powder A-1.

16 Fig. 12 is a graph of the circularity-corresponding diameter of the median powder A-1.

17 Figure 3 is a graph of the particle size distribution of median powder N-1.

18 Figure 4 is a graph of the circularity distribution of median powder N-1.

19 Figure 4 is a plot of the circularity-corresponding diameter of median powder N-1.

20 Fig. 10 is a schematic illustration for describing an example of the image forming method of the present invention.

21 Fig. 12 is a schematic diagram for describing an example of the process cartridge of the present invention.

DESCRIPTION THE PREFERRED EMBODIMENTS

The Inventors have made investigations with respect to the particle diameter and the shape of the toners, and pulverized ones Toner particles, and have discovered that the circularity in particles of 3 μm or larger in diameter in a close way with the transference characteristic and the developing property (image quality) and the fixing property related.

Around about that In addition, the same effect with a toner having particles with different To achieve particle diameters, the circularity must be in particles of 3 μm or larger in diameter be controlled based on the weight average particle diameter of the toner and the proportion of fine powder of 3 μm or smaller In diameter.

If the circularity in particles of 3 μm or larger in diameter is determined on the basis of the weight average particle diameter the toner and the content of fine powder of 3 μm or smaller in diameter, a toner with superior transfer characteristic and can developing property (image quality) and fixing property to be obtained.

If additionally used a special pulverization and classification system For example, the toner of the present invention can be produced by a simple method, which in the conventional method not available yet was.

A pulverization and classification system which enables optimum production of the toner of the present invention is a system in which toner particles are formed from a median powder obtained by;
Melt kneading a mixture containing at least a binder resin, a dye and a sulfur-containing compound, cooling the obtained kneaded product, and then crushing the cooled product by a crushing means;
Introducing the crushed product obtained as a powder material into a first constant speed feeder;
Introducing the powder material in a fixed amount into a mechanical grinding machine from the first constant speed feeder via a powder material inlet of the mechanical grinding machine; the mechanical grinding machine having at least one rotor comprising a rotator connected to the central rotating shaft and a stator located around the rotor, maintaining a certain space between it and the rotor surface, and arranged such that a circular one Space is formed by maintaining the space in an airtight manner;
Rotating the rotor of the mechanical grinding machine at a high speed to finely pulverize the powder material to produce a finely pulverized product having a weight-average particle diameter of 5-12 μm, and containing 70 number percent or less particles of 4.0 μm or smaller particle diameter and 25% by volume or less particles of 10.1 μm or larger particle diameter;
Discharging the finely pulverized product from a powder material discharge port of the mechanical grinding machine and introducing the finely pulverized product into a second constant-speed feeder;
Introducing the finely pulverized product in a predetermined amount into a multi-division gas stream classifier which classifies the powder material using crossed gas streams and the Coanda effect;
Classifying the finely pulverized powder in the multi-division gas stream classifier into at least fine powder, median powder and coarse powder to obtain the median powder; and
Mixing the classified coarse powder with the powder material and introducing it into the mechanical milling machine to perform pulverization and classification to obtain the median powder. The system will be described later.

The provision of toner particles having a small particle diameter results in a large specific surface area of the toner particles. This makes the toner highly agglomerating and adherent. Thus, when the toner image is transferred from the surface of the photosensitive member to the Transfer medium via, or not via, an intermediate transfer member, the force of adhesion may be fixedly applied between the photosensitive member and the toner to lower its transfer efficiency. This tendency is particularly remarkable in the case of toner particles which have been produced by conventional methods of pulverization, which are amorphous and have a polygonal shape.

Also in the case of toners with a small particle diameter that leads Strive to give them an attachment equal or less is more common than that of toners Particle diameter, to improve the transfer efficiency.

The Circular-making of toner particles makes the contact surface between the toner particles and the photosensitive member, and makes possible the transfer efficiency to improve. However, it is very difficult to really spherical toner particles in the case of pulverization toners. Accordingly consider a procedure in which the corners of the toner particles obtained by pulverization are drawn rounded to smooth their surfaces to make them almost spherical do. this makes possible an improvement in transmission efficiency of the toner, however, there are many problems in pulverization inherent, and it was necessary to conduct further investigations.

in the Trap when using low particle diameter toners good point reproducibility can be achieved, but fogging and stains around line images tend to occur. It is considered that this is caused by the inclusion of fine powder and ultrafine powder in a large amount because of fine toner particles are prepared from coarse particles obtained by crushing. toner particles with different particle diameters have different boosting Properties and also have different adhesion. Consequently does that To create a toner with a small particle diameter a toner having a broad distribution of the charge amount. Furthermore this tendency is further remarkable when the charge-controlling material, the added does not, for the purpose of imparting charge to the toner is uniformly dispersed.

The Toner particles produced by pulverization can also be repeatedly classified to obtain a sharp particle size distribution, however, low productivity of the toner may result.

According to the by the inventors performed Investigations, it is important in the toner particles, prepared by pulverization, and in terms of avoiding the occurrence of Waste toner and in terms of achieving a good developing Property, even in a high-temperature and high-humidity environment and a low-humidity environment by improving the transmission efficiency at the time of the transfer the toner image from the surface of the photosensitive member to the transfer medium, that (1) in toner particles with a binder resin and a dye, the Toner particles contain a sulfur-containing compound to to improve the dispersion with other materials to make a toner to be able to have a stable charge amount, and (2) the toner having toner particles generated by Pulverization and classification, by means of a production system, built with a special milling machine and a special one Classifiers in combination, a special particle size distribution and circularity has.

If the sulfur-containing compound is used, it can without Causing any problem to be used. Regarding an improvement in compatibility with other materials at the time of melt-kneading or an improvement of dispersion when Toner particles are made to have a small particle diameter to possess, the compound is preferably pulverized by a known Pulverisierungseinrichtung to a uniform particle diameter to own. The sulfur-containing compound may preferably to be made, a mean particle diameter of 300 microns or less and more preferably 150 μm or less. This allows a further improvement of its compatibility with, and a dispersibility in other materials, and is effective in terms of avoidance of fogging, especially in an environment of lower Humidity.

If the toner is made with a special circularity, For example, a toner is preferred having a weight average particle diameter from 5.0 to 12.0 μm, and further preferred is a toner containing 40% by number or less particles of 4.0 microns or smaller in particle diameter, and 25 volume percent or less particles of 10.1 μm or larger in particle diameter.

When a toner having a weight-average particle diameter larger than 12.0 μm is obtained, For example, its production can be adequately dealt with in terms of the particle diameter by making the charge in the grinding machine as small as possible, or treating materials in a large amount, but the toner particles are so angular in shape that it may become difficult. to bring them to a desired circularity.

If a toner having a weight average particle diameter smaller than 5.0 μm can be obtained with its production in an appropriate manner be handled by making the charge in the grinding machine so as big as possible, or treating the materials in an extremely small amount, but Toner particles are nearly so spherical that it can be difficult can, bring them to the desired circularity to own. About that It can not only be difficult to get them to do that desired circularity but also the fine powder or ultrafine powder can not completely be prevented from occurring. The same applies in relation on the proportion of particles of 4.0 microns or less and particles of 10.1 μm or larger.

• a) die Beziehung zwischen Teilungsrate Z und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (2) genügt: Teilungsrate Z ≤ 5,3 × X (2)vorausgesetzt, dass die Teilungsrate Z durch den folgenden Ausdruck (3) dargestellt ist: Z = (1 – B/A) × 100 (3)wobei A die Partikelkonzentration (Anzahl von Partikeln/μl) der gesamten gemessenen Partikel, wie gemessen mittels eines Durchflusstyp-Partikelbildanalysators FPIA-1000, hergestellt von Toa Iyou Denshi K.K., und B die Partikelkonzentration (Anzahl von Partikeln/μl) von gemessenen Partikeln von 3 μm oder größer im Kreis-entsprechenden Durchmesser ist; und in den Partikeln von 3 μm oder größer im Durchmesser des Toners und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahlbasierenden kumulierten Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (4) genügt: Anzahl-basierender kumulierter Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,51 × X–0,645 (4)vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm bis 12,0 μm ist; oder
• b) die Beziehung zwischen der Teilungsrate Z und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (5) genügt: Teilungsrate Z > 5,3 × X (5);und in den Partikeln von 3 μm oder größer im Durchmesser des Toners und in der Anzahl-basierenden Kreisförmigkeitsverteilung der Kreisförmigkeit a, die Beziehung zwischen dem Anzahlbasierenden kumulierten Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher, und dem massegemittelten Tonerpartikeldurchmesser X dem folgenden Ausdruck (6) genügt: Anzahl-basierender kumulierter Wert Y von Partikeln mit einer Kreisförmigkeit a von 0,950 oder höher ≥ e5,37 × X–0,545 (6)vorausgesetzt, dass der massegemittelte Tonerpartikeldurchmesser X von 5,0 μm bis 12,0 μm ist.

The toner has, in its particles of 3 μm or larger in diameter, particles having a circularity a of 0.900 or higher, as determined according to the following expression (1), in a ratio of 90% or greater as the number-based cumulative value: Circularity a = L 0 / L (1) where L ₀ represents the circumferential length of a circle having the same projected area as a particle image, and L represents the peripheral amount of the particle image;
and where;

• a) the relationship between the division rate Z and the weight-average toner particle diameter X satisfies the following expression (2): Division rate Z ≤ 5.3 × X (2) provided that the division rate Z is represented by the following expression (3): Z = (1-B / A) × 100 (3) where A is the particle concentration (number of particles / μl) of total measured particles as measured by a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and B is the particle concentration (number of particles / μl) of measured particles of 3 μm or larger in the circle-corresponding diameter; and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher and the weight-average toner particle diameter X is as follows (4) satisfies: number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.51 × X -0.645 (4) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm; or
• b) the relationship between the division rate Z and the weight average toner particle diameter X satisfies the following expression (5): Division rate Z> 5.3 × X (5); and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher, and the weight-average toner particle diameter X is as follows Expression (6) satisfies: number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.37 × X -0.545 (6) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm.

The Division rate Z may preferably satisfy 0 <division rate Z ≦ 5.3 × X.

in the If the toner has such a circularity, the Charging the toner can be controlled with ease, and charging can while operation are made uniform and stable. In addition, in case the toner has such a circularity, too found that the toner can be improved in the transfer efficiency. This is because in the case of the toner having such a circularity owns, the contact surface between the toner particles and the photosensitive member low can be made, so that the adhesive power less between the toner particles and the photosensitive element can act. About that In addition, the toner particles have a specific surface area made less than toner produced by the conventional one Collision air grinding machine, and thus the toner has a smaller contact area between the toner particles itself, and the toner powder may have a high bulk density, so that the heat conduction at the time of fixation can be improved to include the Effect of improving the fixing property.

In addition is a case where the particles having a circularity a of 0.900 or higher in the Particles of 3 μm or larger in diameter are present, in a relationship less than 90% as the number-based cumulative value, undesirable because the contact surface between the toner particles and the photosensitive member so is great that the adhesive force of the toner particles is too high on the photosensitive Element can act to achieve sufficient transmission efficiency.

Also undesirable is a case where the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher, the division rate Z and the weight-average particle diameter X satisfies the expression:
Division rate Z ≦ 5.3 × X, preferably 0 <division rate Z ≦ 5.3 × X; but not fulfilled:
Number-based cumulative value Y ≥ e ^5.51 × X ^-0.645 ; that is, a case in which is satisfied:
Number-based cumulative value Y <e ^5.51 × X ^-0.645 ; or a case where the expression is satisfied:
Division rate Z> 5.3 × X; but not satisfied:
Number-based cumulative value Y ≥ e ^5.37 × X ^{-0.545 That} is, a case in which is satisfied:
Number-based accumulated value Y <e ^5.37 × X ^-0.545 . This is because the adhesion of the toner to fixing members and so on tends to occur more, and thus not only can not sufficient transfer efficiency be achieved, but also the toner may have poor fluidity.

When a standard of scattering in the shape of particles with one such circularity, can the circularity standard deviation SD can be used. In the present invention, the circularity standard deviation SD of circularity preferably in the range of 0.030 to 0.050, and more preferably from 0.030 to 0.045.

The mean circularity referred to in the present invention is used as a simple method of expressing the shape of the toner in a quantitative manner. In the present invention, the shape of the particles is measured with a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and the circularity of the particles thus measured is calculated according to the following expression (1). As also shown further in the following expression (5), the value obtained when the total sum of the circularity of all measured particles is divided by the number of all the particles, defined as the mean circularity. Circularity a = L 0 / L (1) where L ₀ represents the circumferential length of a circle having the same projected area as a particle image, and L represents the circumferential length of the particle image.

The circularity standard deviation SD is calculated according to the following equation (6), where the average circularity determined from the above equations (1) and (5) is represented by α , the circularity in each particle is represented by ai, and the number of measured particles is represented by m.

The circularity which is referred to in the present invention is an index, the degree of particle surface rub indicates the toner and the toner particles. It is stated as 1.00 if the particles are perfectly spherical. The more complicated the surface shape is, the lower the value of the circularity. Likewise, the standard deviation SD of the circularity distribution in the present invention, an index indicating the scattering. It indicates that the lower the numerical value, the sharper the distribution own the toner and the toner particles.

The Measuring device "FPIA-1000", which in the present Invention, applies to a calculation method, in in calculating the circularity each particle and then calculating the mean circularity and the circularity standard deviation, circularities from 0.4 to 1.0 divided into 61 divisions, and the middle one circularity and the circularity standard deviation calculated using the central values and frequencies the split points. Between the values of mean circularity and the circularity standard deviation, calculated by this calculation method, and the values of mean circularity and the circularity standard deviation, calculated by the above calculation equation, which is the circularity every particle used directly, only a very small one exists random Error, which is in a degree which is essentially negligible is. Accordingly, In the present invention, such a calculation method in which the concept of the equation of calculation, which the Circularity each Particles used directly, and is used partially modified, for reasons the handling of the data, for example, the calculation period make short, and the operational equation for calculating easy close.

When a special procedure for the measurement is 0.1 to 0.5 ml of a surfactant (preferably Alkyl benzene sulfonate) as a dispersant added to 100 to 150 ml of water, from which impurities have been removed are. To this solution Further, about 0.1 to 0.5 g of a sample to be measured is added added. The resulting dispersion in which the sample has been dispersed is a dispersing treatment by means of an ultrasonic dispersion machine for about 1 to 3 minutes. Adjust the concentration of the dispersion to 12,000 to 20,000 particles / μl and using the above flow type particle image analyzer, become the circularity distribution of particles with circle-corresponding diameters of 0.60 μm to less as 159.21 μm measured. Because the dispersion concentration is adjusted to 12,000 to 20,000 particles / μl, a particle concentration can be maintained that is high is enough to the precision of the analyzer.

The summary of the measurement is described in a catalog of FPIA-1000 (an edition of June, 1995) published by Toa Iyou Denshi KK, and in a manual of the measuring apparatus and Japanese Patent Application Laid-Open No. 8-136439, and is as follows :
The sample dispersion is guided via channels (extending along the flow direction) of a flat flow cell (thickness: about 200 μm). A stroboscope and a CCD (Charge Coupled Device) camera are arranged at positions opposite to each other with respect to the flow cell to form a light path which is cruciform with respect to the thickness of the flow cell. During the flow of the sample dispersion, the dispersion is irradiated with stroboscopic light at intervals of 1/30 second to obtain an image of the particles flowing through the cell so that a photograph of each particle is taken as a two-dimensional image with some Area parallel to the flow cell. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the circle-corresponding diameter. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle, and the peripheral length of the projected image according to the above equation for calculating the circularity.

Of the Structure of the toner, which is preferred in the present invention for the Solve the Tasks will be detailed below described.

The Binder resin usable in the present invention may include vinyl resins, Polyester resins and epoxy resins. Especially preferred are vinyl resins and polyester resins in terms of charging characteristic and the fixing property.

Monomers for the vinyl resins may include styrene; Styrene derivatives such as o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenolstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p- tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and pn-dodecylstyrene; Ethylene-unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and Vinyl fluoride; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; α-methylene-aliphatic monocarboxylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Acrylic esters such as methylacrylate, ethylacrylate, n-butylacrylate, isobutylacrylate, propylacrylate, n-octylacrylate, dodecylacrylate, 2-ethylhexylacrylate, stearylacrylate, 2-chloroethylacrylate and phenylacrylate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether; Vinyl ketones such as methyl vinyl ketone, hexyl vinyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrene, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; Vinylnaphtalene; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; and α, β-unsaturated esters and diesters of dibasic acids. Any of these vinyl monomers may be used alone or in combination of two or more monomers.

among them it is preferred to use monomers in such a combination, which may yield a styrene copolymer and a styrene-acrylic copolymer.

Also usable are polymers or copolymers cross-linked with a crosslinkable monomer as exemplified below.

It can include aromatic divinyl compounds as exemplified by Divivenbenzene and divinylnaphthalene; Diacrylate compounds, connected with an alkyl chain, as exemplified by ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, Neopentyl glycol diacrylate, and the above compounds, their acrylate radical has been replaced with methacrylate; Diacrylate compounds linked to an alkyl chain which contains an ether bond, as exemplified accomplished by diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, Polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, Dipropylene glycol diacrylate, and the above compounds, their acrylate radical has been replaced with methacrylate; Diacrylate compounds linked to a chain which contains an aromatic group and an ether bond, as exemplified by polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, Polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and the above compounds whose acrylate moiety has been exchanged is against methacrylate; and polyester type diacrylate compounds, as exemplified by MANDA (trade name; available at Nippon Kayaku Co., Ltd.).

When polyfunctional crosslinkable monomers may include pentaerythritol triacrylate, Trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, Oligoesteracrylat, and the above compounds, their acrylate radical has been replaced with methacrylate; Triallyl cyanurate, and triallyl trimellitate.

each These crosslinkable monomers may preferably be used in an amount of from 0.01 to 10 parts by weight, and preferably from 0.03 to 5 parts by weight, based on 100 parts by weight of others Monomer.

From These crosslinkable monomers are monomers which are preferably are usable as resins for Toner given the fixing property and the anti-offset properties, aromatic divinyl compounds (especially divinylbenzene) and Diacrylate compounds linked to a chain which is an aromatic Group and contains an ether bond.

In of the present invention optionally a polyurethane, polyvinyl butyral, rosin, a modified Rosin, a terpene resin, a phenolic resin, an aliphatic or alicyclic hydrocarbon resin or an aromatic petroleum resin optionally be mixed with the above binder resin.

in the Trap that uses a mixture of two or more types of resins is as the binder resin, can as a more preferable form, those having various molecular weights preferably mixed in a suitable ratio.

The Binder resin may preferably have a glass transition temperature of 45 to 80 ° C, and more preferably 55-70 ° C, a number average molecular weight (Mn) from 2500 to 50,000, and a weight average molecular weight (Mw) from 10,000 to 1,000,000.

As a method for synthesizing vinyl polymers or vinyl copolymers, any of polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsi be used onspolymerisation. When carboxylic acid monomers or acid anhydride monomers are used, it is preferred to use, in view of the properties of the monomers, bulk polymerization or solution polymerization.

As an example, the following method is available:
By using a monomer such as dicarboxylic acid, dicarboxylic acid anhydride or dicarboxylic acid monoester, a vinyl copolymer can be obtained by bulk polymerization or solution polymerization. In the solution polymerization, the dicarboxylic acid or the dicarboxylic acid monoester may be partially converted to an anhydride by conducting conditions for evaporation at the time of solvent evaporation. Also, the vinyl copolymer obtained by bulk polymerization or solution polymerization may be subjected to a heat treatment to further convert it to an anhydride. The acid anhydride may also be partially esterified with a compound such as an alcohol.

Vice versa For example, the vinyl copolymer thus obtained can be subjected to Hydrolysis treatment to cause its acid anhydride group goes through a ring closure, partially to a dicarboxylic acid to be made.

by the way can be obtained by using a dicarboxylic acid monoester monomer, a divinyl copolymer by suspension polymerization or emulsion polymerization become a heat treatment, to convert it to an anhydride, or may be subjected to a hydrolysis treatment to obtain a dicarboxylic acid an anhydride by ring opening to obtain. A method can be used in which the divinyl copolymer, is dissolved by bulk polymerization or solution polymerization in a monomer, and thereafter a vinyl polymer or copolymer is by suspension polymerization or emulsion polymerization, where a part of the acid anhydride a ring opening goes through, and the dicarboxylic acid unit can be obtained. At the time of polymerization may be another Resin can be mixed in the monomer, and the resulting resin can be subjected to a heat treatment, to make it into an acid anhydride to convict, or the acid anhydride can be esterified by ring-opening Alcohol treatment by treatment with weakly alkaline water.

The dicarboxylic acid or dicarboxylic acid anhydride monomer is strongly alternating copolymerizable and thus is the following Process of one of the preferred methods to a vinyl copolymer in which functional groups such as dicarboxylic acid in a random manner have been dispersed. It is a method in which using a dicarboxylic acid monoester monomer a vinyl copolymer is obtained by solution polymerization, and this Vinyl copolymer is dissolved in the monomer to effect suspension polymerization to the binder resin to obtain. In this process, the whole or the Dicarbonsäuremonoester radical can be converted into an anhydride by alcohol-removing ring opening to an acid anhydride to obtain, under the control of the treatment conditions at the time the solvent evaporation after the solution polymerization. At the time of suspension polymerization, the acid anhydride group goes under a hydrolysis ring opening, and a dicarboxylic acid will be received.

In the transfer into an acid anhydride In the polymer, the infrared absorption of carbonyl shifts a higher one Wavenumber than that of an acid or an ester. Thus, the formation or the disappearance an acid anhydride be determined.

in the thus obtained binder resin are the carboxyl group, the anhydride group and the dicarboxylic acid group uniformly dispersed in the binder resin matrix, and thus can they provide the toner with a good charging feature.

When the binder resin is also preferably a polyester resin below is shown.

In the polyester resin becomes from 45 to 55 mol% of all components supported by an alcohol component, and from 55 to 45 mole% of an acid component.

wobei R darstellt eine Ethylengruppe oder eine Propylengruppe, x und y jeweils eine ganze Zahl 1 oder größer sind, und ein Mittelwert von x + y beträgt 2 bis 10;
ebenso ein Diol, dargestellt durch die folgende Formel (C):

wobei R' darstellt
-CH₂CH₂-,

Glycerin, Sorbitol und Sorbitan.As the alcohol component, it may include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2 Ethyl 1,3-hexanediol, hydrogenated bisphenol A, a bisphenol derivative represented by the following formula (B):

wherein R represents an ethylene group or a propylene group, each of x and y is an integer of 1 or greater, and an average of x + y is 2 to 10;
also a diol represented by the following formula (C):

where R 'represents
-CH ₂ CH ₂ -,

Glycerine, sorbitol and sorbitan.

When a dibasic carboxylic acid ingredient, the holds 50 mol% or more of the total acid component may include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic and phthalic anhydride, and their anhydrides; Alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, and their anhydrides, as well as succinic acid, which further substituted is with an alkyl group or alkenyl group having 6 to 18 carbon atoms, or their anhydrides; unsaturated dicarboxylic acids like fumaric acid, maleic acid, citraconic and itaconic acid, and their anhydrides. As a tribasic or higher carboxylic acid can to include it trimellitic acid, pyromellitic benzophenonetetracarboxylic and their anhydrides.

One Particularly preferred alcohol component of the polyester resin the bisphenol derivative represented by the above formula (B). When the acid component Particularly preferred are dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and their anhydrides, succinic acid, n-dodecenylsuccinic acid or their anhydrides, fumaric acid, maleic and maleic anhydride; and tricarboxylic acids like trimellitic acid or their anhydrides.

One Toner containing the polyester resin used as a binder resin from this acid component and Alcohol component, has good fixing property and superior Anti-offset properties as toner for hot roller fixing.

The Polyester resin may preferably have an acid value of 90 mg · KOH / g or lower, and more preferably 50 mg · KOH / g or lower, and may preferably have an OH value (hydroxyl value) of 50 mg · KOH / g or lower, and more preferably 30 mg · KOH / g or less. This is the case because a polyester resin with a large number of molecular group terminal groups the charging characteristic of the Toners can cause a large environmental dependency to own.

The Polyester resin may preferably have a glass transition temperature from 50 to 75 ° C, and more preferably from 55 to 65 ° C, and also preferably have a number average molecular weight (Mn) of from 1500 to 50 000, and more preferably from 2000 to 20,000. The polyester resin may preferably have a weight average molecular weight (Mw) from 6,000 to 100,000, and more preferably from 10,000 to 90,000.

(2) Maleimid-Derivat:

(3) Styrol-Derivat:

(gebunden an der ortho-Position oder der para-Position)The sulfur-containing polymer or sulfur-containing copolymer used in the present invention as the sulfur-containing compound is added mainly as a charge controlling agent. The sulfur-containing compound may preferably be a polymer or copolymer containing a sulfonic acid group, and a monomer unit having the sulfonic acid group. Such a monomer may include styrylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, methacrylic sulfonic acid, maleic acid amide Deri vat having the following structural formula (1), a maleimide derivative represented by the following structural formula (2), and a styrene derivative having the following structural formula (3). (1) maleic acid amide derivative:

(2) maleimide derivative:

(3) styrene derivative:

(bound to the ortho position or the para position)

monomers for producing the above sulfur-containing polymer or copolymer can lock in Vinyl type polymerizable monomers. Usable are monofunctional polymerizable monomers and polyfunctional polymerizable Monomers.

The monofunctional polymerizable monomers may include styrene; Styrene derivatives such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; polymerizable monomers of the acrylate type such as Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate and 2-benzoyloxyethyl acrylate; polymerizable monomers of the methacrylate type such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; Methylene aliphatic monocarboxylate; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl benzoate and vinyl format; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether; and vinyl ketones such as methyl vinyl ketone, hexyl vinyl ketone and isopropyl vinyl ketone.

The polyfunctional polymerizable monomers may include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis [4- (acryloxydiethoxy) phe nyl] propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis [4- (methacryloxy · diethoxy) phenyl] propane, 2,2'-bis [4- (methacryloxy polyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene and divinyl ether.

The above polymers can be prepared by a process which includes bulk polymerization, solution, Emulsion polymerization and suspension polymerization. in view of operability and so on, solution polymerization is preferred.

The Counter ion of the polymer having a sulfonic acid group may be a hydrogen ion, a sodium ion, a potassium ion, a calcium ion or an ammonium ion. It may furthermore be preferred to use a hydrogen ion.

In of the present invention, among the above polymers having a sulfonic acid group, For example, it is particularly preferable to use a copolymer of a styrenic monomer and an acrylic monomer having a sulfonic acid-containing acrylamide monomer (this means Sulfonic acid group-containing Copolymer).

The Styrene monomer and acrylic monomer used in such a sulfonic acid group-containing Copolymer, may be suitably chosen are made of vinyl monomers for producing the above-described vinyl copolymer. You can preferably include a combination of styrene with acrylate, or styrene with methacrylate.

The Sulfonic acid group-containing Acrylamide monomer which is used in the sulfonic acid group-containing Copolymer, may include 2-acrylamide propanesulfonic acid, 2-acrylamide-n-butanesulfonic acid, 2-acrylamide-n-hexanesulfonic acid, 2-acrylamide-n-octanesulfonic acid, 2-acrylamide-n-dodecanesulfonic acid, 2-acrylamide-n-tetradecane-sulfonic acids, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylphenylethanesulfonic acid, 2-acrylamido-2- (4-chlorophenyl) propanesulfonic acid, 2-acrylamido-2-carboxymethylpropanesulfonic acid, 2-acrylamido-2- (2-pyridine) propanesulfonic acid, 2-acrylamide-1-methylpropanesulfonic acid, 3-acrylamide-3-methylbutanesulfonic acid, 2-methacrylamide-n-decanesulfonic acid, and 2-methacrylamide-n-tetradecane-sulfonic acids. It may preferably include 2-acrylamido-2-methylpropanesulfonic acid.

Of the Polymerization initiator used when the sulfur-containing Polymer or sulfur-containing copolymer is prepared suitably chosen are used by initiators, which are used if the above Vinyl copolymer is synthesized. Peroxide type initiators may preferably be used.

In Referring to the process for synthesizing the sulfur-containing species Polymers or sulfur-containing copolymers are not particular Restrictions. Any method of solution polymerization, Suspension polymerization and bulk polymerization can be used become. Preference is given to solution polymerization, which performs a copolymerization in an organic solvent, which contains a lower alcohol.

The Copolymerization of the styrene monomer and the acrylic monomer with the Sulfonic acid-containing Acrylamide monomer may preferably be in a weight ratio of Styrene monomer and acrylic monomer: sulfonic acid-containing acrylamide monomer = 98: 2 to 80:20. A case where the sulfonic acid-containing acrylamide monomer in a relationship is less than 2% by weight, is undesirable because the toner is not can have sufficient charging feature. A case in which it in a ratio greater than 20% by weight is undesirable because the toner is a may have unstable environmental stability.

The Sulfur-containing polymer or sulfur-containing copolymer may preferably have an acid value of from 3 to 80 mg · KOH / g, more preferably from 5 to 40 mg · KOH / g, and more preferably from 10 to 30 mg · KOH / g. If it's an acidity which is less than 3 mg · KOH / g, it may be a low Have charge control effect, and also the toner can a have low environmental stability. If there is one acid value owns, the higher is 80 mg · KOH / g, The toner tends to be from water in a high temperature, high humidity environment to be affected and to have low environmental stability.

The sulfur-containing polymer or sulfur-containing copolymer may be a weight average Molecular weight (Mw) of 2,000 to 200,000, preferably from 17,000 to 100,000, and more preferably from 27,000 to 50,000 possess. A case in which it has a weight-average molecular weight (Mw) less than 2,000 is undesirable because the sulfur-containing polymer or sulfur-containing copolymer can mutually melt or finely dispersed in the binder resin, so that the charging properties are difficult can be improved to cause a lowering of the fluidity or the transfer performance of the toner. A case in which it has a weight-average molecular weight (Mw) greater than 200,000 is undesirable because the sulfur-containing polymer or sulfur-containing copolymer can phase separate from the binder resin and become completely detached from toner particles to cause fogging or fogging To reduce the environmental stability.

The Sulfur-containing polymer or sulfur-containing copolymer may preferably have a glass transition point (Tg) of 30 to 120 ° C, far preferably from 50 to 100 ° C, and still more preferably from 70 ° C up to 95 ° C. A case where the sulfur-containing polymer or sulfur-containing Copolymer a glass transition point (Tg) lower than 30 ° C has, is undesirable, because the toner has low fluidity and storage stability can, and also a poor transmission performance can own. A case where there is a glass transition point (Tg) higher than Has 120 ° C, is undesirable, because the toner may have a low fixing property in the case of images with a high percent toner toner percentage (image area percentage).

The Sulfur-containing polymer or sulfur-containing copolymer may preferably have a volatile content of 0.01% to 2.0%, and more preferably from 0.01 to 1.0% or less. The work a fleeting one Less than 0.01% requires a complicated step eliminating the fleeting Share. If it's a fleeting one Has a proportion of more than 2.0%, the toner can be used in a high-temperature high-humidity environment can be slightly charged, in particular little charged triboelectrically be left after standing. The fleeting one Proportion of the sulfur-containing polymer or sulfur-containing Copolymer corresponds to the ratio loss in mass or weight when heated for one hour at high temperature (135 ° C).

The Sulfur-containing polymer or sulfur-containing copolymer may preferably have a "melt index value" (MI value): g / 10 minute from 0.1 to 200, and more preferably from 0.2 to 150. When it has a MI value less than 0.1, the polymer or Copolymer have a low compatibility with the binder resin, to tend to be non-uniformly dispersed in toner particles so that the toner has a broad distribution of the charge quantity can. If it has a MI value greater than 200, the polymer or copolymer can melt so sharply, that the toner may have low anti-blocking properties, to have a low multi-blade mileage. The MI value is measured by a method described in JIS K7210 method A. Thereafter, the measurements obtained are calculated in the 10-minute value.

It There are no particular restrictions on the method of extraction the sulfur-containing polymer or sulfur-containing copolymer from the toner, and any method can be used.

(A) "Molecular weight and molecular weight distribution of " Sulfur-containing polymer or sulfur-containing copolymer are measured by GPC (gel permeation chromatography) in the following Wise.

Columns are stabilized in a heat chamber at 40 ° C. Through the columns maintained at this temperature, THF (tetrahydrofuran) is run as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a sample of THF solution is injected to make a measurement. In measuring the molecular weight of the sample, the molecular weight distribution attributed to the sample is calculated from the relationship between the logarithmic value and the number of times of counting a calibration curve prepared by using plural kinds of monodisperse polystyrene standard samples. As standard polystyrene samples used for the preparation of the calibration curve, it is suitable to use samples having molecular weights of 10 ² to 10 ⁷ , which are available, for example, from Toso Co., Ltd. or Showa Denko KK, and to use at least 10 standard polystyrene samples. An RI (refractive index) detector is used as a detector. Columns should be used in combination with a variety of commercially available polystyrene gel columns. For example, they may preferably comprise a combination of Shodex GPC KF-801, KF-802, KF-803, KF-804, KF-805, KF-806, KF-807 and KF-800P available from Showa Denko KK; or a combination of TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ) and TSK Guard Column he available from Toso Co., Ltd.

The Sample is prepared in the following manner.

The Sample is added in tetrahydrofuran (THF), and is allowed to stand for several hours let stand for a long time, followed by thorough shaking to to be mixed well with the THF (until the coalescent substance of the Sample has disappeared), which continues for at least 12 hours is left standing. Here, the sample is thus in THF at least 24 hours left altogether. Thereafter, the solution, which is about a probebehandelnden Filter (pore size: 0.45 up to 0.5 μm; for example MAISHORIDISK-25-5, available from Toso Co., Ltd. or EKIKURODISK 25CR, available from German Science Japan, Ltd., can be used) is filtered used as a sample for the GPC. The sample will be like this set that they contain resin components in a concentration of 0.5 to 5 mg / ml.

(B) The "glass transition point" of the sulfur-containing Polymer or sulfur-containing copolymer is determined by Measurement by DSC (Differential Scanning Calorimetry).

In the DSC measurement, given the principle of measurement, becomes the measurement preferably performed with a high precision Differential scanning calorimeter. For example, it can be used DSC-7 manufactured by Perkin Elmer Co.

The Measurement is performed according to ASTM D3418-82. During execution the measurement, the temperature is raised once and then lowered, to record a flow and then the temperature is raised at a temperature of 10 ° C / min, and the DSC curve, which is thus is obtained is used.

(C) The "acid value" of the sulfur-containing Polymer or sulfur-containing copolymer is determined in the following way. The fundamental Operation is in accordance with JIS K0070 carried out.

The Number of milligrams of potassium hydroxide required is present to neutralize the free fatty acids or resin acids in 1 g of sample, the acidity value called (or acid number). A test is performed in the following manner.

(1) Reagent

• (a) Solvent: An ethyl ether / ethyl alcohol mixed solution (1 + 1 or 2 + 1) or a benzene / ethyl alcohol mixed solution (1 + 1 or 2 + 1) used. These solutions are each neutralized maintained with an N / 10-potassium hydroxide-ethyl alcohol solution below Use of phenolphthalein as an indicator, just before use.
• (b) Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
• (c) N-10 potassium hydroxide-ethyl alcohol solution: 7.0 g of potassium hydroxide will be dissolved in water, used in an amount as low as possible, and Ethyl alcohol (95 v / v%) is added to make 1 liter of solution, which is allowed to stand for 2 to 3 days, followed by filtration. Standardization is performed in accordance with JIS K-8006 (basic Details related to titration during one Reagent content test).

(2) workflow

1 up to 20 g of sample become precise weighed, and 100 ml of the solvent and a few drops of the phenolphthalein solution as indicator are added solution will be thorough afterwards shaken, until the sample is complete disbanded is. In the case of a solid sample it is dissolved by heating over a water bath. After cooling becomes the resulting solution titrated with the N / 10-potassium hydroxide-ethyl alcohol solution, and the time when the indicator is gently red for 30 seconds, is considered as the endpoint of neutralization.

(3) calculation

The acid value is calculated according to the following equation. A = (B × f × 5.611) / S in which;
A is the acid value;
B is the amount (ml) of N / 10 potassium hydroxide-ethyl alcohol solution used;
f is the factor of the N / 10 potassium hydroxide ethyl alcohol solution; and
S is the sample (g).

(D) The "hydroxyl value" of the sulfur-containing Polymer or sulfur-containing copolymer is determined in the following way. The fundamental Expiration is performed according to JIS K0070.

The Number of milligrams of potassium hydroxide required for the Neutralization of hydroxy group-bound acetic acid when 1 g of a sample acetylated by a prescribed method is the hydroxy value (or hydroxy number) is called. A test is carried out using the following reagent and calculation expression.

(1) Reagent

• (a) Acetylating reagent: 25 g of acetic anhydride is placed in a 100 mL volumetric flask and pyridine is added to a 100 ml solution to surrender, followed by thorough shake (optionally, pyridine can be added further). The acetylation reagent is stored in a brown bottle so that it does not come into contact with moisture or a vapor of carbon dioxide or acid.
• (b) Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
• (c) N / 2 potassium hydroxide ethyl alcohol solution: 35 g potassium hydroxide disbanded in water, used in an amount that is as low as possible and ethyl alcohol (95 v / v%) is added to make 1 liter of solution, which is allowed to stand for 2 to 3 days, followed by filtration. Standardization is performed in accordance with JIS K-8006.

(2) workflow

From 0.5 to 2.0 g of the sample becomes precise weighed in a round bottom flask, and add 5 ml of the acetylation reagent added. A small funnel is attached to the opening of the piston, and its Ground is immersed by about 1 cm in a 95 to 100 ° C warm Glycerin bath, and heated. Here, around the neck of the piston from heating by the heat of the To detain baths, the bottom of the neck of the piston is covered with a cardboard disc, provided in the middle with a round hole. An hour later the piston is taken out of the bath. After being left to cool 1 ml of water added over the funnel, followed by shaking, to decompose acetic anhydride. To complete the decomposition effect, the flask is again for 10 minutes in Glycerinbad heated. After leaving to cool become the walls of the funnel and flask, washed with 5 ml of ethyl alcohol, followed by titration with the N / 2-potassium hydroxide-ethyl alcohol solution Use of phenolphthalein solution as a reagent. Here, a blind test is performed parallel to the main test. If necessary, a KOH-THF solution can be used as an indicator.

(3) Calculation:

The hydroxyl value is calculated from the following equation. A = [(B - C) × f × 28.05] / S + D in which
A is the hydroxy value;
B is the amount (ml) of the N / 2 potassium hydroxide-ethyl alcohol solution used in the blank test;
C is the amount (ml) of the N / 2 potassium hydroxide-ethyl alcohol solution used in the main test;
f is the factor of the N / 2 potassium hydroxide ethyl alcohol solution;
S is the sample (g); and
D is the acid value.

The sulfur-containing polymer or sulfur-containing copolymer may be used as such. In view of an improvement in compatibility with, and dispersion in, other materials, it is preferred to pulverize the polymer or copolymer by means of a known pulverizer to have a uniform particle diameter. Thus, particles formed by pulverization may preferably have an average particle diameter of 300 μm or less, and more preferably 150 μm or less. This allows good dispersion in other materials and especially the prevention of fog with respect to image quality.

The Sulfur-containing polymer or sulfur-containing copolymer may be contained in an amount of 0.01 to 15 parts by weight, preferably from 0.1 to 10 parts by weight, and more preferably from 0.5 to 8 parts by weight.

If the sulfur-containing polymer or sulfur-containing copolymer is present in a proportion of less than 0,01 parts by weight, can have a sufficient charge control effect only with difficulty be achieved. If it is in a proportion of more than 15 parts by weight There may be low compatibility with others Own materials, or may unwanted excess charge in a low-humidity environment provide.

Of the Proportion of the sulfur-containing polymer or sulfur-containing Copolymer in the toner can be measured by capillary electrophoresis or similar.

Of the Toner of the present invention to its charging property more stable, can be used optionally in combination with another charge control agent. Such an extra Charge control agent may preferably be used in one Amount of 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the binder resin.

The additional Charge control agent may include the following.

When Charge control agent, capable of To control the toner so that it is negatively chargeable are organic Metal complexes or chelate compounds are available which include monoazometal complexes, Metal complexes of aromatic hydroxycarboxylic acids and metal complexes of aromatic dicarboxylic acids. Close next to it they are an aromatic hydroxycarboxylic acid, aromatic mono- or polycarboxylic and metal salts thereof, anhydrides thereof or esters thereof, and phenol derivatives like bisphenol.

Charge control agent capable of Controlling the toner that it is positively chargeable include a nigrosine and modified products of nigrosine modified with a fatty acid metal salt; quaternary Ammonium salts such as tributylbenzylammonium 1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate; Onium salts such as phosphonium salts of these, and, as chelated pigments of these, triphenylmethane dyes and lake pigments of these (lake-forming substances may include phosphotungstic acid, phosphomolybdic acid, phosphotungstic-molybdic acid, tannic acid, lauric acid, ferricyanides and ferrocyanides); Metal salts of higher fatty acids; Diorganotin oxides as Dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; and diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate.

If the toner of the present invention is used as a magnetic toner is a magnetic material is used as a dye. The magnetic material, inserted in magnetic toner, may include iron oxides such as magnetite, hematite and ferrite, and iron oxides which include other metal oxides; metals such as iron, cobalt and nickel, or alloys of any of these metals with another metal such as aluminum, cobalt, copper, lead, magnesium, Nickel, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, Manganese, selenium, titanium, tungsten and vanadium, and mixtures of these.

In particular, the magnetic material may include triiron tetraoxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), Gadolinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymium iron oxide (NdFe ₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O _4), manganese iron oxide (MnFe ₂ O _4), lanthanum iron oxide (LaFeO _3), iron powder (Fe), cobalt powder (Co) and nickel powder (Ni). Any of the above magnetic materials may be used alone or in combination of two or more. A particularly preferred magnetic material is fine powder of triiron tetraoxide or γ-iron sesquioxide.

These magnetic materials may preferably be those having an average particle diameter of 0.05 to 2 μm, and a coercive force of 1.6 to 12.0 kA / m, a saturation magnetization of 50 to 200 Am ² / kg (preferably 50 to 100 At ² / kg) and a residual magnetization of 2 to 20 Am ² / kg, as magnetic properties using a magnetic field of 795.8 kA / m.

The magnetic material can be used in an amount of 10 to 200 parts by weight, and preferably from 20 to 150 parts by weight, based on 100 parts by weight of the binder resin.

When Non-magnetic dyes usable in the toner of the present invention Invention, can all suitable pigments or dyes are used. As pigments are usable carbon black, aniline black, acetylene black, Naphthol Yellow, Hanza Yellow, Rhodamine Varnish, Alizarin Varnish, Red Iron Oxide, Phthalocyanine Blue and Indanthren blue. Any of these can be added in an amount of 0.1 part by weight to 20 parts by weight, and preferably from 1 to 10 parts by weight based on 100 parts by weight of the binder resin. Suitable dyes are anthraquinone dyes, Xanthene dyes and Methine dyes, any of these can be added in an amount of 0.1 part by weight to 20 parts by weight, and preferably from 0.3 to 10 parts by weight, based on 100 parts by weight of the binder resin.

In The present invention may include at least one type of release agent optionally inserted in the toner particles. The release agent may include the following.

aliphatic Hydrocarbon waxes such as low molecular weight polyethylene, Low molecular weight polypropylene, microcrystalline wax and paraffin wax, oxides of aliphatic hydrocarbon waxes such as polyethylene wax oxide, and block copolymers of these; waxes, mainly composed from a fatty acid ester, such as carnauba wax, sazol wax and montan acid ester waxes; and such, obtained by subjecting a part or whole of a fatty acid ester a deoxidation treatment, such as deoxidized carnauba wax. It can also include saturated straight chain fatty acids like palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid and parinaric; saturated Alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, Ceryl alcohol and melissyl alcohol; long-chain alkyl alcohols; polyvalent Alcohols such as sorbitol; fatty acid amides like linoleic acid amide, oleic and lauric acid amide; saturated fatty acid bisamides such as methylenebis (stearic acid amide), Ethylenebis (capric), Ethylenebis (lauric acid amide) and hexamethylene bis (stearic acid amide); unsaturated fatty acid amides such as ethylenebis (oleinamide), Hexamethylene bis (oleic acid amide), N, N'-dioleyladipic acid amide and N, N'-dioleyl sebacic acid amide; aromatic bisamides such as m-xylenebis (stearic acid amide) and N, N'-distearylisophthalamide; Fatty acid metal salts (what is commonly called metal soap) such as calcium stearate, calcium laurate, Zinc stearate and magnesium stearate; Graft wax obtained by graft polymerization vinyl monomers such as styrene or acrylic acid to fatty acid hydrocarbon waxes; partially esterified products of polyhydric alcohols with fatty acids, such as monoglyceride behenate; and methyl esterified products having a hydroxy group by hydrogenation of vegetable fats and oils.

The Release agent may preferably be used in an amount from 0.1 to 20 parts by weight, and more preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

The Release agent becomes common added in the binder resin by a method in which a resin in a solvent disbanded and raising the temperature of the resin solution, the release agent added is mixed and mixed with stirring, or a method in they are mixed at the time of kneading in binder resin added to become.

One fluidity can be added become the toner of the present invention. The fluidity improver is a substance that can improve the fluidity of the toner by its external Addition to the toner particles, as viewed in comparison before and after its addition. For example, it may include Fluororesin powder such as fine vinylidene fluoride powder and fine polytetrafluoroethylene powder; fine silica powder such as wet process silica and Dry-process silica, and hydrophobic fine silica powder obtained by subjecting this fine silica powder surface treatment with a silane coupling agent, a titanium coupling agent or a silicone oil.

A preferred fluidity improver is dry process fine silica powder or fine fumed silica powder prepared by vapor phase oxidation of a silicon halide. For example, it is a method which applies heat decomposition oxidation reaction in an oxyhydrogen frame of silicon tetrachloride gas. The reaction proceeds essentially as follows. SiCl 4 + 2H 2 + O 2 → SiO 2 + 4HCl

In In this production step, it is also possible to use another metal halide to use, such as aluminum chloride or titanium chloride, together with the silicon halide, a fine composite powder of silicon dioxide to obtain with other metal oxide. In terms of its particle diameter is preferred to use fine silica powder with a middle primary Particle diameter within the range of 0.001 to 2 microns, and in particular preferably within the range of 0.002 to 0.2 μm.

Commercially available fine silica powders prepared by vapor-phase oxidation of silicon halides include, for example, those marketed under the following trade names.
Aerosil 130, 200, 300, 380, TT600, MOX170, MOX80, COK84 (Aerosil Japan, Ltd.);
Ca-O-SiL M-5, MS-7, MS-75, HS-5, EH-5 (CABOT CO.);
Wacker HDK N20, V15, N20E, T30, T40 (WACKER-CHEMIE GMBH);
DC Fine Silica (Dow Corning Corp.); and
Fransol (Franzil Co.).

It It is also preferable to use hydrophobic fine silica powder obtained by hydrophobing the fine silica powder, produced by vapor-phase oxidation of a silicon halide. The hydrophobic fine silica powder, in particular prefers a fine silica powder, which treated so its hydrophobicity, measured by methanol titration test, shows a value within the range of 30 to 80.

In Regarding the methods of hydrophobing, the fine silica powder made hydrophobic by chemical treatment with an organosilicon compound, the capable is to react with, or physically adsorb the fine Silica. As a preferred method, the fine Silica powder produced by vapor phase oxidation of a Silicon halide, treated with an organosilicon compound become.

The Organosilicon compound may include hexamethyldisilazane, trimethylsilane, Triethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, Methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, Triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and Dimethylpolysiloxane having 2 to 12 siloxane units per molecule, and containing a hydroxy group attached to each Si in its units at the terms. It may also include silicone oils such as dimethylsilicone oil. each of these may be used alone or in the form of a mixture of two or more species.

As fluidity improvers, such good results ensure that they have a specific surface area of 30 m ² / g or greater, preferably 50 m ² / g or greater, and more preferably from 80 to 400 m ² / g, as measured by the BET method Use of nitrogen absorption. The fluidity improver may preferably be used in an amount of 0.01 to 8 parts by weight, and preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner.

In the present invention, other inorganic fine powder may be externally added to the toner particles. Such an inorganic fine powder usable in the present invention may include a compound represented by the following formula: [M ₁ ] _a [Ti] _b O _c wherein M ₁ represents a metallic element selected from the group consisting of Sr, Mg, Zn, Co, Mn, Ca, Ba and Ce; a represents an integer of 1 to 9; b represents an integer of 1 to 9; and c represents an integer of 3 to 9.

Strontium titanate (SrTiO ₃ ) and calcium titanate (CaTiO ₃ ) are particularly preferred because the effect of the present invention is more apparent.

The inorganic fine powder used in the present invention may preferably be, for example, a powder prepared by producing a material by sintering, and mechanically pulverizing the material, followed by air classification to obtain the desired particle size distribution to sit.

The inorganic fine powder can be added in an amount of 0.1 to 10 parts by weight, and preferably from 0.2 to 8 parts by weight, based on 100 parts by weight of the toner particles. A case in to which it was added being in an amount less than 0.1 parts by weight is undesirable because no adequate cleansing property or polishing property can be shown opposite Rest toner, paper guide and ozone deposits remaining on the photosensitive member. A case in which it added will be bigger in a lot than 10 parts by weight, is undesirable because fogging easily occurs, or the surface of the Photosensitive element in an excessive manner abraded can be.

The inorganic fine powders used in the present invention may have a weight average particle diameter of 0.2 up to 4 μm, and preferably from 0.5 to 3 μm. A case where it has a weight-average particle diameter less than 0.2 μm, is undesirable, because no sufficient polishing effect can be obtained. A case in which it has a weight average particle diameter of greater than 4 μm, is not preferred, because fogging easily occurs or that destroyed photosensitive element can be.

One preferred method for producing the toner of the present invention Invention becomes detailed described with reference to the accompanying drawings.

1 and 2 are examples of a flow chart showing an overview of the toner manufacturing process. As shown in the flowcharts, the toner manufacturing process is characterized in that it does not require a classification step before the pulverization treatment and the pulverization step, and the classification step is performed in one go.

In The toner production becomes a mixture that contains at least the binder resin, the dye and the sulfur-containing compound, melt-kneaded to obtain a kneaded product. After that cooled product cooled is the cooled Product crushed by means of a crushing Facility to a crushed To obtain product which is used as a powder material. Thereafter, the powder material is first in a fixed Quantity in a mechanical grinding machine with at least one rotor introduced, which is a rotator, attached to the central rotating shaft, and a stator, which is located around the rotor, while maintaining a certain space between itself and the rotor surface; the Grinder is constructed so that a circular space is created by Maintaining the space, airtight. The rotor of the mechanical Grinding machine is rotated at a high speed to the powder material to finely pulverize (the product to be pulverized). After that will the finely pulverized powder material introduced in a classification step and is classified there to get a classified product serving as a toner base material comprising a group of Particles with the prescribed particle size. Here, in the classification step, may preferably be used as a classifying device a multi-part gas flow classifier with at least one coarse powder region, one median powder region and a fine powder region. For example, if a triple-division gas stream classifier is used, the powder material is at least classified in three fractions of fine powder, median powder and coarse powder. in the Classifying step making use of such a classifier, is the coarse powder, consisting of a group of particles with Particle diameters, larger as the desired Particle size, and Fine powder consisting of a group of particles with particle diameters, smaller than the desired one Particle size, and the median powder (toner particles) is mixed with the inorganic fine powder described above and an external one Additive such as hydrophobic colloidal silica, and thereafter as Toner used.

Ultra fine powder consisting of a group of particles with particle diameters, less than the desired one Particle size, becomes ordinary reused by feeding in the step of melt kneading for producing the powder material, comprising toner materials to be introduced in the step of Pulverization, or discarded.

3 and 4 show examples of a system unit to which the above toner production method has been applied. The method will be further described below in detail with reference to this drawing. As the toner base material powder material introduced into this system unit, a colored resin particle powder containing at least the binder resin, the dye and the sulfur-containing compound is used. As the powder material, a material obtained by, for example, melt-kneading the mixture comprising the binder resin, the dye and the sulfur-containing compound, cooling the obtained kneaded product, and further crushing the cooled product is used a crushing device.

In this system unit, the toner base material powder material is introduced in a fixed amount in a mechanical milling machine 301 , which is the pulverizing device, via a first constant speed feeder 315 , The powder material introduced therein is immediately pulverized by means of the mechanical grinding machine 301 , and then introduced into a second food processor 2 constant speed ( 54 in 3 ) over a collecting cyclone 229 ( 53 in 3 ). Then, over a vibrating food processor 3 ( 55 in 3 ) and further via a material supply nozzle 16 ( 148 in 3 ), it is introduced into a multi-division gas flow classifier 1 ( 57 in 3 ), which is the classifier.

In this system unit, the relationship between the set amount of the powder material introduced from the first constant-speed feeder can be determined 315 into the mechanical milling machine 301 , which is the pulverizer, and the predetermined amount of the powder material introduced by the second constant-speed feeder 2 ( 54 in 3 ) into the multi-division gas stream classifier 1 ( 57 in 3 ), which is the classifying means, are preferably set from 0.7 to 1.7, more preferably from 0.7 to 1.5, and still more preferably from 1.0 to 1.2, assuming that the former is 1 Amount of powder material introduced by the first constant speed feeder 315 into the mechanical milling machine 301 , This is preferred in view of the productivity and production efficiency of the clay.

The gas stream classifier is commonly used as a component unit of a system unit in which correlated equipment is connected via communicating devices such as pipes. In the in 3 The system unit shown is a multi (triple) division classifier 57 (the in 8th classifiers shown), a second constant speed feeder 54 , a vibrating food processor 55 , a collecting cyclone 59 , a collecting cyclone 60 and a collecting cyclone 61 connected via communicating facilities. Also in the in 4 shown system unit a multi (triple) division classifier 1 (the in 9 classifiers shown), a food processor 2 constant speed, a vibrating food processor 3 , a collecting cyclone 4 , a collecting cyclone 5 and a collecting cyclone 6 connected via a communicating device.

In this system unit, in the case of 4 , the material powder is fed into the constant speed feeder 2 via a suitable device, and then introduced into the triple division classifier 1 from the vibrating food processor 3 via the material supply nozzle 16 , When introduced, the material powder may preferably be introduced into the triple division classifier 1 at a flow rate of 10 to 350 m / second. The classification chamber of the triple division classifier 1 is usually constructed in a size of [10 to 50 cm] × [10 to 50 cm] so that the material powder can be classified immediately in 0.1 to 0.01 second or less in three or more groups of particles. Thereafter, the material powder is classified by the triple division classifier 1 into the group of larger particles (coarse particles), group of median particles and group of smaller particles. Thereafter, the group of larger particles is guided via a discharge guide tube 11a , sent to and collected in the collecting cyclone 6 , and sent back to the mechanical milling machine 301 , The group of median particles outside the classifier discharge via the discharge tube 12a , and collected in the collecting cyclone 5 to be used as a toner. The group of smaller particles is discharged outside the classifier via the discharge tube 13a and collected in the collecting cyclone 4 where they are reused by feeding in the step of melt-kneading to make the powder material comprising the toner materials, or discarded. The collecting cyclones 4 . 5 and 6 may also be operative as suction evacuation means for aspirating the material powder to the classifying chamber via the material supply nozzle 16 , Also, the group of larger particles that are classified here may preferably be reintroduced into the first constant speed feeder 315 to be mixed in the powder material and to be pulverized again by the mechanical grinding machine 301 ,

As in 3 shown, the larger particles (coarse particles), which can be returned to the first feeder constant speed 315 from the multi-division gas stream classifier 57 to be introduced, preferably reintroduced in an amount of from 0 to 10.0 weight percent, and more preferably from 0 to 5.0 weight percent, based on the weight of the finely powdered product fed from the second feed apparatus 54 constant speed. This is preferred in view of the productivity of the toner. When the larger particles (coarse particles) return to the first feeder constant speed 315 can be reintroduced by the multi-division gas stream classifier in an amount greater than 10.0 weight percent, the dust in the mechanical Mahlma machine 301 in such a large concentration that the unit itself can receive a large charge and at the same time the toner particles can be excessively pulverized at the time of pulverization to easily undergo surface deterioration due to heat or to cause an on-machine melt adhesion. This is undesirable in view of the productivity of the toner.

As in 4 shown, the larger particles (coarse particles), classified in the multi-division gas stream classifier 1 , are more preferably introduced into a third food processor 331 constant speed, and then introduced from the third food processor 331 constant speed into the mechanical grinding machine 301 , This is further preferred in view of the productivity of the toner. Here, the larger particles (coarse particles), classified in the multi-division gas stream classifier 1 , are preferably recycled to the third constant-speed food processor 331 in an amount of 0 to 10.0 weight percent, and more preferably from 0 to 5.0 weight percent, based on the weight of the finely pulverized product supplied from the second feed apparatus 2 constant speed. This is preferable in view of the productivity of the toner. When the larger particles (coarse particles) are recycled to the third feeder 331 constant speed of the multi-division gas flow classifier 1 , to be recycled in an amount greater than 10.0 weight percent, the dust must be in such a high concentration in the mechanical grinding machine 301 that the unit itself can receive a large load, and at the same time the toner particles can be excessively pulverized at the time of pulverization to easily undergo surface deterioration due to heat, or to cause an on-machine melt-adhesion. This is undesirable in view of the productivity of the toner.

In In this system, the powder material may preferably be such Have particle size, that mesh number -18 (ASTM E-11-61) Particles in a ratio from 95 to 100 weight percent and 100 mesh (ASTM E-11-61) Particles in a ratio from 90 to 100 weight percent.

In this system unit, to obtain the toner having the weight-average particle diameter of 5.0 to 12.0 μm, and preferably 5.0 to 10 μm, having a sharp particle size distribution, the finely pulverized product obtained by the mechanical grinding machine 301 , preferably have a weight average particle diameter of 5.0 to 12.0 μm, and contain 70% by number or less, more preferably 65% by number or less, particles of 4.00 μm or less, and 25% by volume or less, more preferably 15% by volume or less, particles of 10.1 μm or larger. Also, the median powder obtained by classification may preferably have a weight-average particle diameter of 5 to 12 μm and contain 40% by number or less, more preferably 35% by number or less, particles of 4.00 μm or smaller, and 25% by volume or less, more preferably 15% by volume or less, particles of 10.1 μm or larger.

In the above system unit, which is the manufacturing method of the toner of the present invention, the system requires no first classification step before the pulverization treatment, and the pulverization step and the classification step may be described in a train become.

A mechanical grinding machine, preferably used as the pulverization device, used in the manufacturing process for the toner of the present invention Invention will be described. The mechanical grinding machine can include for For example, a grinding machine Inomizer, manufactured by Hosokawa Micron K.K .; a milling machine KTM, manufactured by Kawasaki Heavy Industries, Ltd .; and Turbo mill, manufactured by Turbo Kogyo K.K. These machines are used as such, or may preferably be used after being suitably modified.

In particular, may be used a mechanical grinding machine, as in 5 to 7 shown. This enables easy pulverization treatment of the powder material, and thus the improvement of the efficiency can be advantageously achieved.

In the 5 to 7 The mechanical grinding machine shown will be described below. 5 is a schematic cross-sectional view of an example of the mechanical grinding machine. 6 is a schematic cross-sectional view taken along the line 6-6 in FIG 5 , 7 is a perspective view of a rotor 314 , shown in 5 , This device is composed of, as in 5 shown a housing 313 , a serving 316 a distributor 220, a rotor 314 who is in the case 3 composed of a rotator mounted on a central rotating shaft 312 rotatable at a high speed, and provided with a high number of furrows on its surface, a stator 310 which is arranged while maintaining a certain space along the periphery of the rotor 314 . and provided with a high number of furrows on its surface, a material feed opening 311 for introducing the material to be treated, and also a material discharge opening 302 for unloading the powder which has been treated.

The Pulverization using the mechanical milling machine, the As described above, for example performed in the following manner.

The powder material is charged in a prescribed amount to the mechanical grinding machine from its material supply port 311 where the powder material is introduced into a pulverization chamber prechamber 212 , and is immediately pulverized by the action of i) the impact caused between the rotor 314 which rotates at a high speed in the pulverization chamber, and provided with a high number of furrows on its surface, and the stator 310 provided with a high number of furrows on its surface; ii) a high number of ultrahigh velocity vortices caused by this impact; and iii) the high frequency pressure vibration caused by such vortices. Thereafter, the powder material is discharged by passing through the material discharge opening 302 , The air transporting the material particles is discharged outside the system unit via a pulverization chamber rear chamber 320 , and over the material discharge opening 302 , a tube 219 , a collecting cyclone 229 , a bag filter 222 , and a suction fan 224 , In the present invention, the powder material is pulverized in this way, and thus the desired pulverization can be carried out with ease, without increasing the fine powder and the coarse powder.

When the powder material is pulverized by the mechanical grinding machine, cold air may preferably be sent into the mechanical grinding machine by a cold air generating means 321 together with the powder material. The cold air may also preferably have a temperature of 0 to -18 ° C. Also, as an on-machine cooling means of the main structure of the mechanical grinding machine, the mechanical grinding machine may be constructed to have the structure of the casing 316 , and cooling water (or preferably an antifreeze such as ethylene glycol) may be allowed to pass. Also, by using the above cooling unit and the cladding structure, the chamber temperature T1 of the pulverization chamber pre-chamber (swirl chamber) 212 which is communicated to the powder material supply inlet in the mechanical grinding machine, preferably controlled to 0 ° C or below, preferably from -5 to -15 ° C, and more preferably from -7 to -12 ° C. This is preferred in view of the productivity of the toner. Controlling the chamber temperature T1 of the vortex chamber 212 in the mechanical milling machine at 0 ° C or below, preferably from -5 to -15 ° C, and more preferably from -7 to -12 ° C, toner particles can prevent from undergoing surface deterioration due to heat, and enables pulverization of the powder material in a good efficiency. A case where the chamber temperature T1 of the swirl chamber in the mechanical grinding machine is higher than 0 ° C. is undesirable in view of the productivity of the toner because the toner particles are liable to undergo surface deterioration due to heat at the time of pulverization or cause on-machine melt adhesion. Also, in an attempt to operate at such a temperature that the chamber temperature T1 of the swirl chamber in the mechanical milling machine is less than -15 ° C, the refrigerant (an alternative chlorofluorocarbon) used in the cold air generating device 321 , Are exchanged for a chlorofluorocarbon.

At present, the elimination of chlorofluorocarbons is under way from the point of view of protecting the ozone layer. The use of a chlorofluorocarbon in the cold air generating device 321 is undesirable in the face of the ecological problems of the entire earth.

The alternative chlorofluorocarbons may include R134A, R404A, R407C, R410A, R507A, and R717A. Of these, R404A becomes special preferred considering the benefits of energy saving and the Safety.

The cooling water (or preferably an antifreeze such as ethylene glycol) is supplied to the enclosure from a cold water supply port 317 , and is discharged via a cold water discharge opening 318 ,

The finely pulverized product produced in the mechanical milling machine is discharged via the powder material discharge port 302 over the posterior chamber 320 the mechanical milling machine. Here, the chamber temperature T2 at the posterior chamber 320 The mechanical grinding machine can be controlled at 30 to 60 ° C. This is preferred in view of the productivity of the toner. Controlling the chamber temperature T2 at the rear chamber 320 The mechanical milling machine at 30 to 60 ° C, the toner particles from keep from undergoing surface deterioration due to heat, and can enable pulverization of the powder material in a good efficiency. A case in which the chamber temperature T2 at the posterior chamber 320 The mechanical grinding machine is lower than 30 ° C is undesirable in view of the property of the toner, because there is a possibility that the material is not pulverized to have caused a short passage. A case where T2 is higher than 60 ° C is also undesirable in view of the productivity of the toner, because there is a possibility that the material has been excessively pulverized at the time of pulverization to easily deteriorate the surface deterioration due to heat or the on-machine fusion adhesion to cause.

When the powder material is pulverized by the mechanical grinding machine, the chamber temperature T1 at the swirl chamber 212 , and the chamber temperature T2 at the posterior chamber 320 preferably, are controlled to be in a temperature difference ΔT (T2-T1) of 40 to 70 ° C, more preferably 42 to 67 ° C, and still more preferably 45 to 65 ° C. This is preferred in view of the productivity of the toner. Controlling ΔT between the temperature T1 and the temperature T2 of the mechanical grinding machine to from 40 to 70 ° C, more preferably from 42 to 67 ° C, and still more preferably from 45 to 65 ° C, can prevent the toner particles from entering a Surface deterioration due to heat, and can allow pulverization of the powder material in a good efficiency. A case where ΔT between the temperature T1 and the temperature T2 of the mechanical grinding machine is lower than 40 ° C is undesirable in view of the property of the toner because there is a possibility that the material is not pulverized to cause a short passage to have. A case in which ΔT is larger than 70 ° C is also undesirable in view of the productivity of the toner, because there is a possibility that the material has been excessively pulverized at the time of pulverization, surface deterioration due to heat, or on-machine fusion adhesion easy to cause.

Also, when the powder material is pulverized by the mechanical milling machine, the binder resin may preferably have a glass transition point (Tg) of 45 to 75 ° C, and more preferably 55 to 65 ° C. Also, with respect to Tg, the chamber temperature T1 at the swirl chamber 212 the mechanical grinding machine is 0 ° C or less, and may be lower than Tg by 60 to 75 ° C. This is preferred in view of the productivity of the toner. Controlling the chamber temperature T1 at the vortex chamber 212 For example, in the mechanical grinding machine at 0 ° C or lower, or at 60 to 75 ° C lower than Tg, the toner particles may prevent from undergoing surface deterioration due to heat, and may allow pulverization of the powder material with good efficiency. Also, the chamber temperature T2 at the posterior chamber 320 The mechanical grinding machine preferably at 5 to 30 ° C, and more preferably 10 to 20 ° C, be lower than Tg. Controlling the chamber temperature T2 at the posterior chamber 320 The mechanical grinding machine so as to be lower by 5 to 30 ° C, and more preferably 10 to 20 ° C, as Tg, can prevent toner particles from undergoing surface deterioration due to heat, and can enable pulverization of the powder material with good efficiency ,

The rotor 314 may preferably be rotated at a peripheral speed of 80 to 180 m / sec, more preferably 90 to 170 m / sec, and still more preferably 100 to 160 m / sec. This is preferred in view of the productivity of the toner. Rotate the rotor 314 preferably at a peripheral speed of 80 to 180 m / sec, more preferably 90 to 170 m / sec, and still more preferably 100 to 160 m / sec, the powder material may be prevented from being insufficiently pulverized or excessively pulverized , and allows pulverization of the powder material in a good efficiency. A case in which the rotor 314 Rotating at a peripheral speed lower than 80 m / sec is undesirable in view of the property of the toner because the material tends not to be pulverized to cause a short passage. A case in which the rotor 314 rotating at a peripheral speed higher than 180 m / sec is also undesirable in view of the productivity of the toner because the unit itself can receive a high charge and at the same time the toner particles can be excessively pulverized at the time of pulverization to tend to to cause surface deterioration due to heat or to cause an on-machine melt adhesion.

The space between the rotor 314 and the stator 310 may preferably be set to a minimum gap of 0.5 to 10.0 mm, more preferably 1.0 to 5.0 mm, and still further 1.0 to 3.0 mm. Set the space between rotor 312 and the stator 310 preferably to a gap of from 0.5 to 10.0 mm, more preferably from 1.0 to 5.0 mm, and still more preferably from 1.0 to 3.0 mm, the powder material can prevent it from being insufficiently pulverized, or To be excessively pulverized, and allows pulverization of the powder material in a good efficiency. A case in which the space between the rotor 314 and the stator 310 is greater than 10.0 mm is undesirable in view of the property of the toner, because the material tends not to be pulverized to cause a short passage chen. A case in which the space between the rotor 314 and the stator 310 is less than 0.5 mm is also undesirable in view of the productivity of the toner because the unit itself can receive a large charge and at the same time the toner particles can be excessively pulverized at the time of pulverization to easily undergo surface deterioration due to heat , or to cause an on-machine melt adhesion.

This pulverization method does not require primary classification before the step of pulverization, and may be of simple construction. In addition, it does not require a large amount of air for pulverizing the powder material. Thus, the amount of consumed electric energy per kilogram of the toner in the step of pulverization may be about 1/3 or less, as compared with the case of producing toners using the inks 13 shown conventional collision air grinding machine, thus the energy costs can be kept low.

Of the Gas flow classifier will be described below.

As an example of a preferred multi-division gas stream classifier, a device of the shape as in FIG 9 shown (cross-sectional view) shown as a specific example.

As in 9 shown form a sidewall 22 and a G-block 23 a part of a classifying chamber, and classifying edge blocks 24 and 25 each have classifying edges 17 and 18 , The G-block 23 is slidable right and left for its adjustment position. Likewise are the classifying edges 17 and 18 each swinging around the shafts 17a and 18a , and thus the position of the peak of each classifying edge can be changed by the swinging of the classifying edge. The corresponding classifying edge blocks 24 and 25 are positioned so that their positions can slide right and left. When pushed, the classifying edges become 17 and 18 of the kind of an edge of a knife also pushed to the right and left. These classifying edges 17 and 18 share a classification zone 30 the classifying chamber 32 in three sections.

A material feed nozzle 16 which at its rearmost end a material feed opening 40 has for introducing a material powder, which has at its rearmost end a high-pressure air nozzle 41 and a material powder guide nozzle 42 , and also with a nozzle in the classifying chamber 32 , located on the right side of the side wall 22 , and a Coanda block 26 is located along the extension of the lower tangential line of the material feed nozzle 16 to form a long elliptical arc. The classifying chamber 32 has a block forming the left part 27 , provided with an air intake edge 19 of the shape of an edge of a knife, which expands the classifying chamber 32 opposite, and further provided with air intake tubes 14 and 15 on the left side of the classifying chamber 32 leading to the classifying chamber 32 to open. Likewise, as in 4 shown are the air intake tubes 14 and 15 provided with a first gas supply control device 20 and a second gas supply control device 21 , which include, for example, a damper, and also provided with static pressure gauges 28 and 29 ,

The positions of the classifying edges 17 and 18 , the G-block 23 and the air intake edge 19 are adjusted according to the type of toner particles, the material powder to be classified and also according to the desired particle size.

At the bottom, the side wall and the top of the classifying chamber 32 there are discharge openings 11 . 12 and 13 which open to the classifying chamber according to the respective divided zones. The discharge openings 11 . 12 and 13 are connected to communicating devices such as tubes, and may each be provided with closing means such as valve means.

The material feed nozzle 16 includes a rectangular tube portion and a pyramidal tube portion, and the ratio of the inner diameter of the rectangular tube portion to the inner diameter of the narrowest portion of the pyramidal tube portion can be set from 20: 1 to 1: 1, preferably from 10: 1 to 2: 1 by one to get good feed rate.

The classification in the multi-split classifying zone having the above structure is operated in the following manner, for example. The interior of the classifying chamber is evacuated via at least one of the discharge openings 11 . 12 and 13 , The material powder is blasted and dispersed into the classifying chamber 32 via the material feed nozzle 16 at a flow rate of preferably from 10 to 350 m / sec, using the gas flow which flows at a reduced pressure over the Way inside the opening of the material feed nozzle 16 into the classifying chamber 32 , and using the ejection effect of compressed air blasted from the high pressure air nozzle 41 ,

The particles in the material powder that enter the classifying chamber 32 has been given, are moved to draw curves, through the effect, the Coanda effect of the Coanda block 26 and the action of gases such as air flowing in at the same time, and are classified according to the particle size and the inertial force of the individual particles in such a manner that larger particles (coarse particles) are classified to the outside of the gas flow, ie the first one Section on the outer side of the classifying edge 18 , Median particles are classified to the second section, defined between the classifying edges 18 and 17 and smaller particles are classified to the third section on the inner side of the classifying edge 17 , The larger particles classified by classification, the median particles classified by classification, and the smaller particles classified by classification are respectively discharged from the discharge openings 11 . 12 and 13 discharged.

In the above classification of the material powder, the grading points mainly depend on the positions of the tips of the grading edges 17 and 18 with reference to the lower end of the Coanda block 26 at which end the material powder is blasted out into the classifying chamber 32 , The classification points are also affected by the suction flow rate of the classification gas streams or the velocity of the material powder being blasted outward from the material supply nozzle 16 ,

In addition, in the multi-division gas flow classifier with the shape as in 9 shown, the material feed nozzle 16 , the material powder guide nozzle 42 and the high pressure air nozzle 41 provided at the upper end of the multi-division gas stream classifier, and the classifying edge classifying edge blocks are set positionally changeable so that the classifying zone can be changed in shape. Thus, the classifier can be more improved in classification efficiency than any conventional gas stream classifier.

Various physical properties shown in the following examples, are measured by methods as described below.

(1) Measurement of Particle Size Distribution:

The Particle size distribution can be measured by different means. In the present invention It is measured with a Coulter Counter Multisizer.

One Coulter Counter Multisizer Model II (manufactured by Coulter Electronics, Inc.) is called a used measuring instrument. An interface (made by Nikkaki K.K.), which outputs the number distribution and the volume distribution, and a personal computer CX-1 (manufactured by Canon, Inc.) connected. As an electrolytic solution, an aqueous one-percent Sodium chloride solution prepared using pure sodium chloride. Measurement is carried out by adding as a dispersant from 0.1 to 5 ml of a surface-active Substance (preferably alkylbenzenesulfonate) to from 100 to 150 ml of above aqueous Electrolyte solution, and further adding from 2 to 20 mg of a sample to be measured. The electrolyte solution, in which the sample has been suspended, becomes for about 1 minute to about 3 Minutes in an ultrasonic dispersion machine subjected to a dispersion. Measurement is performed with the above Coulter counter Multisizer Model II, using as an aperture an aperture of 100 μm, when the particle diameter of the toner is measured, and one Aperture of 13 μm, when the particle diameter of inorganic fine powder is measured becomes. The volume and number of toner and inorganic Fine powder is measured, and the volume distribution and the number distribution are being calculated. Then the weight-based mass-averaged Particle diameter, determined from the volume distribution, determined.

(2) Measurement of a glass transition point (Tg) of the toner and toner particles:

Measured according to ASTM D3418-82, using a differential heat analyzer (DSC measuring Instrument) DSC-7, manufactured by Perkin Elmer Co.

A sample for measurement is precisely weighed within the range of 5 to 20 mg, preferably 10 mg. This sample is placed in a pan made of aluminum and an empty aluminum pan is used as reference. The measurement is carried out in a normal temperature-normal humidity at a heating rate of 10 ° C / min within the measuring temperature range of 30 to 200 ° C. In the course of this heating, main peak endothermic peaks are obtained in the temperature range of 40 to 100 ° C. The point at which the line intersects at a middle point of the baseline before and after the appearance of the endothermic peak thus obtained and the differential thermal curve is regarded as the glass transition point Tg.

(3) Measurement of molecular weight distribution of the binder resin material:

molecular weight a chromatogram is measured by GPC (gel permeation chromatography) under the following conditions.

Become pillars stabilized in a heat chamber from 40 ° C. The columns held at this temperature produce tetrahydrofuran (THF) as a solvent run at a flow rate of 1 ml / min. A sample is dissolved in THF and then filtered with a filter of 0.2 microns in pore size, and the resulting filtrate is used as a sample. From 50 to 200 μl of a THF sample solution of a Resin, which has been regulated to a sample concentration to possess from 0.05 to 0.6 weight percent, is injected to to take the measurement. When measuring the molecular weight of the sample is the molecular weight distribution attributed to the sample is calculated from the relationship between the logarithmic value and the count number a calibration curve made using several Types of monodisperse polystyrene standard samples. As standard polystyrene samples, used to make the calibration curve, it is suitable To use samples with molecular weights of 600, 2100, 4000, 17500, 51000, 110,000, 390000, 860000, 2000000 and 4480000 which available are from Pressure Chemical Co. or Toso Co., Ltd., and at least about 10 standard polystyrene samples to use. An RI (refractive index) detector is used as a detector.

In Respect to the columns, to be precise Measurement in the range of molecular weight from 1,000 to 2,000,000 is carried out preferably, several commercially available polystyrene gel columns in Combination to use. For example, they may preferably comprise a combination of μ-Styragel 500, 1000, 10000 and 100000 available by Waters Co., and Shodex KA-801, KA-802, KA-803, KA-804, KA-805, KA-806 and KA-807 available by Showa Denko K.K.

An example of the image-forming method of the present invention will be described below with reference to FIG 20 described.

The surface of a photosensitive drum 701 is negatively charged by a contact charging device 742 , which is a primary charging device, and illuminates with laser light 705 to generate a digital-latent image by image scanning. The latent image thus formed is developed by reverse development using a dry process magnetic toner (one-component type developer) 710 which is in a developing unit 709 is worn with a magnetic blade 711 and a developing sleeve 704 , internally provided with a magnet. In the developing zone, the conductive substrate becomes the photosensitive drum 701 grounded, and an alternating voltage, a pulse voltage and / or DC voltage is applied to the developing sleeve 704 about a voltage-applying device 712 , A transfer paper P is supplied and transported to the transfer zone where the transfer paper P is electrostatically charged by a contact transfer device 702 on its rear surface (the surface opposite to the photosensitive drum side) via a voltage applying device 723 so that the toner image on the surface of the photosensitive drum 701 is transferred to the transfer paper P via the contact transfer device 702 , The transfer paper P separated from the photosensitive drum 701 is subjected to fixing using a heat pressure roller fixing assembly 707 to fix the toner image on the transfer paper P. The toner image may be transferred from the photosensitive drum 701 on the transfer paper P via an intermediate transfer member, or may be transferred to the transfer paper P via an intermediate transfer member.

The dry process magnetic toner remains on the photosensitive drum 701 after the step of transfer, is removed by a cleaning device 708 with a cleansing blade. If the remaining dry process magnetic toner 704 is present in a small quantity, the purifying step may be omitted. After cleaning, the residual toner on the surface of the photosensitive drum 701 eliminated by erase exposure 706 Thus, the procedure is repeated starting from the charging step using the contact charging device 742 , repeated.

The photosensitive drum 701 (That is, the electrostatic image-bearing member) comprises a photosensitive layer and a conductive substrate, and is rotated in the direction of an arrow. The evolving sleeve 704 Produced on a non-magnetic cylinder which is a toner-carrying member is rotated so as to move in the same direction as the movement of the surface of the photosensitive drum 701 in the developing zone. Inside the developing sleeve 704 There is a multipolar permanent magnet (magnetic roller) serving as a magnetic field generating means in an unrotatable state. The dry process magnetic toner 710 , kept in the developing unit 709 , is coated on the surface of the developing sleeve 704 , and, for example, negative triboelectric charges are imparted to the magnetic toner as a result of the friction between the surface of the developing sleeve 704 and the magnetic toner. A magnetic doctor 711 made of iron is also located near the cylinder surface (space: 50 μm to 500 μm) to face a magnetic pole position of the multipolar permanent magnet. Thus, the thickness of the magnetic toner layer is controlled to be small (30 μm to 300 μm) and uniform, so that a magnetic toner layer having a thickness smaller than the distance between the photosensitive drum 701 and the developing sleeve 704 is generated in the developing zone. The rotational speed of this developing sleeve 704 is controlled so that the peripheral speed of the developing sleeve 704 substantially equal to or close to the peripheral speed of the photosensitive drum 701 is. As the magnetic spreader 711 may be used a permanent magnet instead of iron to form an opposite magnetic pole. In the developing zone, an AC voltage or a pulse voltage may be applied to the developing sleeve 704 via a voltage device 712 , This AC voltage may have a frequency (f) of 200 to 4000 Hz and a Vpp of 500 to 3000 V.

When the magnetic toner is moved in the developing zone, the magnetic toner moves to the electrostatic latent image side by the electrostatic force of the photosensitive drum surface 70 and the effect of the AC voltage or pulse voltage.

Instead of the magnetic doctor blade 711 For example, an elastic blade formed of an elastic material such as silicone rubber may be used to regulate the layer thickness of the magnetic toner layer by pressure to coat the magnetic toner on the developing sleeve.

21 illustrates a specific example of the process cartridge of the present invention. In the process cartridge, at least the developing means and the electrostatic image-bearing member are connected in a unit as a cartridge, and the process cartridge is detachably mounted in the structure of the image-forming apparatus (for example, a copying machine or a laser printer).

In 21 is a process cartridge 750 exemplified in which an evolving device 709 a drum type electrostatic image bearing member (a photosensitive drum) 701 , a cleaner 708 with a cleansing blade 708a and a primary charging device (a charging roller) 742 are connected in a unit.

In the in 21 The process cartridge shown has the developing device 709 in a toner container 760 an elastic blade 711a and a magnetic toner 710 , At the time of development, a prescribed electric field is generated opposite to the photosensitive drum 701 and the developing sleeve 704 by applying a voltage from a voltage applying device. For the developing step to be preferably carried out, the distance between the photosensitive drum is 701 and the developing sleeve 704 very important.

The present invention will be described below in detail by way of examples and comparative examples of the invention. Sulfur-containing copolymer Preparation Example 1 (by weight) methanol 300 parts toluene 100 parts styrene 480 parts 2-ethylhexyl acrylate 78 parts 2-acrylamide-2-methylpropane 42 parts lauroyl 6 parts

The The above materials were placed in a flask and a stirrer Thermometer and a nitrogen inlet were installed. solution was carried out at 70 ° C in a nitrogen atmosphere, which was continued for 10 hours until the polymerization reaction was finished. The polymer thus obtained was reduced under reduced pressure Dried and then crushed to a sulfur-containing To obtain copolymer (a) having a weight-average molecular weight Mw of 27000, a glass transition temperature Tg of 73 ° C and a mean particle diameter of 420 μm. Physical Properties of the sulfur-containing copolymer (a) are shown in Table 1.

Sulfur-containing copolymer

Preparation Examples 2 and 3

Sulfur-containing Copolymers (b) and (c) as shown in Table 1 were obtained in the same manner as in Production Example 1 of the sulfur-containing Copolymer with the exception that the composition ratio of modified polymers used therein has been.

Sulfur-containing copolymer

Preparation Examples 4 and 5

The sulfur-containing copolymer (a) was polymerized by means of a 1 mm disk speed mill, and a jet mill to obtain a sulfur-containing copolymer (d) having an average particle diameter of 290 μm, and a sulfur-containing copolymer (e). having an average particle diameter of 150 μm, shown in Table 1. Sulfur-containing copolymer Production Example 6 (by weight) methanol 300 parts toluene 100 parts styrene 468 parts 2-ethylhexyl acrylate 90 parts 2-acrylamide-2-methylpropane 42 parts lauroyl 6 parts

Sulfur-containing copolymer (f) as shown in Table 1 was obtained in the same manner as in Production Example 1 except that the above materials were used. Physical properties of the sulfur-containing copolymer (f) are shown in Table 1. Sulfur-containing copolymer Preparation Example 7 (by weight) methanol 300 parts toluene 100 parts styrene 470 parts 2-ethylhexyl acrylate 90 parts 2-acrylamide-2-methyl propane sulfonic acid 40 parts lauroyl 10 parts

The above materials were placed in a 2 liter flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet tube. Solution polymerization was carried out at 65 ° C for 10 hours while stirring and feeding in nitrogen. The contents were taken out of the flask and dried under reduced pressure, and then crushed by means of a hammer mill to obtain sulfur-containing copolymer (g) having the physical properties shown in Table 1. Sulfur-Containing Copolymer Preparation Example 8 (by weight) methanol 100 parts toluene 300 parts styrene 470 parts 2-ethylhexyl acrylate 90 parts 2-acrylamide-2-methylpropane 40 parts lauroyl 12 parts

Sulfur-containing copolymer (h) having the physical properties shown in Table 1 was obtained in the same manner as in Production Example 6 except that the above materials were used. Sulfur-containing copolymer Preparation Example 9 (by weight) methanol 300 parts toluene 100 parts styrene 550 parts 2-acrylamide-2-methylpropane 50 parts lauroyl 12 parts

Sulfur-containing copolymer (i) having the physical properties shown in Table 1 was obtained in the same manner as in Production Example 6 except that the above materials were used. Sulfur-containing copolymer Preparation Example 10 (by weight) methanol 300 parts toluene 100 parts 4-t-butylstyrene 570 parts methacrylsulfonic 30 parts lauroyl 10 parts

Sulfur-containing copolymer (j) having the physical properties shown in Table 1 was obtained in the same manner as in Production Example 1 except that the above materials were used. Sulfur-containing copolymer Preparation Example 11 (by weight) methanol 300 parts toluene 100 parts styrene 560 parts 2-acrylamide-2-methyl propane sulfonic acid 40 parts lauroyl 12 parts

Sulfur-containing copolymer (k) having the physical properties shown in Table 1 was obtained in the same manner as in Production Example 6 except that the above materials were used. Sulfur-containing copolymer Preparation Example 12 (by weight) styrene 510 parts n-butyl acrylate 66 parts methacrylsulfonic 24 parts

Using the above materials, bulk polymerization was conducted for 8 hours while heating at 120 ° C without adding any polymerization solvent and polymerization initiator. Thereafter, 300 parts by weight of xylene was added and the reaction mixture was cooled to 110 ° C, and 300 parts by weight of xylene with 6 parts by weight of t-butylperoxy-2-ethylhexanoate dissolved therein was added dropwise for 6 hours, which was continued for 2 hours until the polymerization reaction was finished. The polymer thus obtained was dried under reduced pressure and then crushed to obtain sulfur-containing copolymer (1) having the physical properties shown in Table 1. Sulfur-containing copolymer Preparation Example 13 (by weight) methanol 100 parts 2-butanone 300 parts styrene 470 parts 2-ethylhexyl acrylate 90 parts 2-acrylamide-2-methylpropane 40 parts 2,2-Acobis (2-methylbutyronitrile) 6 parts divinylbenzene 0.05 parts

Sulfur-containing copolymer (m) having the physical properties shown in Table 1 was obtained in the same manner as in Production Example 1 except that the above materials were used. example 1 Binder resin (polyester resin, Tg: 60 ° C, acid value: 20 mg · KOH / g, hydroxyl value: 30 mg · KOH / g, molecular weight, Mp: 7000, Mn: 3000, and Mw: 55000) 100 parts Magnetic iron oxide (average particle diameter: 0.20 μm, properties under application of a magnetic field of 795.8 kA / m, Hc: 9.2 kA / m, σs: 82 Am ² / kg and σr: 11.5 Am ² / kg 90 parts Sulfur-containing copolymer (a) 2 parts Ethylene-propylene copolymer of low molecular weight 3 parts

The above materials have been thoroughly mixed using a Henschel stirrer (FM-75 type, manufactured by Mitsui Miike Engineering Corporations), and then kneaded using a twin-screw kneader (PCM-30 type, manufactured from Ikegai Corp.) set at a temperature of 130 ° C. The obtained kneaded product was cooled and then crushed by means of a hammer mill to a size of 1 mm or smaller to obtain powder material (A) (crushed product).

The powder material (A) was finely pulverized and classified by the system unit shown in FIG 4 , Turbo Mill Model T-250, (manufactured by Turbo Kogyo KK) was used as a mechanical grinding machine 301 , The distance between the rotor 314 and the stator 310 , shown in 5 , was set to 1.5 mm, and the rotor 314 was operated at a peripheral speed of 115 m / sec.

In the present example, the powder material consisting of a crushed product is placed in the mechanical grinding machine 301 over the first food processor 315 table-type constant speed at a speed of 20 kg / h, and pulverized there. That in the mechanical milling machine 301 Powdered powder material is collected by a cyclone 229 , accompanied by intake air, pulled by a vacuum blower 224 , and then introduced into a second food processor 2 constant speed. Here, the inlet temperature in the mechanical milling machine was -10 ° C, the outlet temperature was 46 ° C, and ΔT between the inlet temperature and the outlet temperature was 56 ° C. Also, the finely pulverized product A obtained here was obtained by pulverization using the mechanical milling machine 301 , a weight average particle diameter of 6.6 μm, and had a sharp particle size distribution containing 53% by number of particles of 4.0 μm or smaller in particle diameter and 5.4% by volume of particles of 10.1 μm or larger in particle diameter.

Next, finely pulverized product A was obtained by pulverization using the mechanical milling machine 301 introduced into the second constant speed feeder 2 and then introduced into the multi-division gas stream classifier 1 with which as in 9 shown construction, via the vibrating filling apparatus 3 and the material feed nozzle 16 at a speed of 22 kg / h. In the multi-division gas stream classifier 1 For example, the finely pulverized product is classified into three fractions, coarse powder, median powder and fine powder, using the Coanda effect. When the finely pulverized product was introduced into the multi-division gas stream classifier 1 , the interior of the classifier chamber was evacuated over at least one of the discharge openings 11 . 12 and 13 where the gas flows, which are inside the material supply nozzle 16 flow, with an opening in the classifying chamber, was used by the action of evacuation, and also the compressed air, blasted from the high-pressure air supply nozzle 41 , has been used. The thus-introduced finely pulverized product was classified into three fractions, coarse powder G, median powder A-1 and fine powder, immediately in 0.1 second or shorter. Among them, obtained by classification, the coarse powder G was collected by the collecting cyclone 6 , After that it was introduced into the mechanical grinding machine 301 at a rate of 1.0 kg / h, and repeatedly introduced into the pulverization step.

The Median powder A-1 (magnetic toner particles), thus obtained by classification in the above classification step, had a weighted average Particle diameter of 6.5 μm and had a sharp particle size distribution that contained 20.5 number percent particles of 4.0 μm or smaller in particle diameter, and 3.8% by volume of particles of 10.1 μm or larger in particle diameter.

Here, the ratio of the weight of the finally obtained median powder (magnetic toner to the total weight of the introduced powder material (ie, classification yield) 82%.

To 100 parts by weight of this median powder A-1, 1.2 parts by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) was externally added using a Henschel stirrer to obtain an insulating negatively-chargeable Magnetic toner (A).

Of the Magnetic toner (A) had a weight average particle diameter of 6.5 μm. Measurement with FPIA-1000 at the magnetic toner (A) revealed that it contained 95.7% by weight particles with a circularity a from 0.900 or higher, and 78.4 number percent of particles having a circularity a of 0.950 or higher. As well was the particle concentration A before the cut of the particles of 3 μm or smaller (the total particles) 15209 particles / μl, and the particle concentration B of the measured particles of 3 microns or greater 13028.3 particles / μl.

The particle size distribution, circularity distribution, and circle-related diameter, measured with FPIA-1000, are plotted in FIG 14 to 16 ,

Evaluation 1

The dry process magnetic toner (A) was put in a developing unit of a copying machine NP6350 manufactured by CANON INC. Using the electrophotographic method shown in FIG 20 , and was allowed to stand overnight (12 hours or longer) in a normal temperature-normal humidity chamber (23 ° C / 50% RH). After measuring the weight of the developing assembly, the developing assembly was inserted into the NP6350 and its developing sleeve was rotated for 3 minutes. Here, the cleaner part and the waste toner collection part in the main body were detached and their weight was previously measured. Using a measurement protocol with a print percentage (image area percentage) of 6%, images were reproduced on 500 sheets to evaluate the toner transfer efficiency. The transfer efficiency of the magnetic toner (A) was 96%.

The transmission efficiency was calculated according to the following calculation expression. Transfer efficiency (%) = [{developing unit weight loss - (weight increase in cleaner part + weight increase in waste toner collection part} / weight loss of developing unit] × 100

Evaluation 2

After this the above transfer efficiency was measured, the copying machine with the developing assembly moves to a normal temperature low humidity chamber (23 ° C / 5% RH). Thereafter, the developing assembly was removed from the copier and let stand for three days. After that, the developing one became Assembly inserted into a NP6350, and the developing sleeve was rotated for a minute. Using a measurement protocol with a percent pressure (Image area percentage) of 6%, images were reproduced on 1000 sheets to evaluate the images on the basis of fog on white surfaces during the test. The Ranking of the evaluation is shown below.

• A: Schleierbildung beträgt weniger als 0,1%.
• B: Schleierbildung beträgt 0,1% oder mehr, bis weniger als 0,5%.
• C: Schleierbildung beträgt 0,5% oder mehr, bis weniger als 1,5%.
• D: Schleierbildung beträgt 1,5% oder mehr, bis weniger als 2,0%.
• E: Schleierbildung beträgt 2,0% oder mehr.

Using a fog-measuring, reflection-measuring instrument REFLECTOMETER (manufactured by Tokyo Denshoku KK), the reflectance at the white areas of the image and that of the untouched paper was measured, and a difference between them is considered to be fogging. Reflectance of virgin paper - reflection on white surfaces = haze (%)

• A: fogging is less than 0.1%.
• B: fogging is 0.1% or more, to less than 0.5%.
• C: fogging is 0.5% or more, to less than 1.5%.
• D: fogging is 1.5% or more, to less than 2.0%.
• E: fogging is 2.0% or more.

Evaluation 3

Of the Magnetic toner (A) was used in a copier NP6085, manufactured by CANON INC., and images were reproduced at 100000 Scroll in a normal temperature low humidity chamber (23 ° C / 5% RH), where the image density (F) of the last images was previously measured. Thereafter, the developing assembly was detached from the copier and stand left in a high temperature high humidity chamber (32.5 ° C / 85% RH) for 2 days. Here was as a measure for preventing moisture condensation in the developing Building unit, the developing unit in a plastic bag locked when she was put in the high temperature high humidity chamber. After conditioning temperature and humidity for 5 hours or longer the bag open and the developing assembly was taken out. The evolving one Assembly was incorporated into the NP6085, and its developing sleeve became Rotated for 1 minute. After that, images were reproduced to 10 Scroll, and an average of the image densities on the 10 sheets was considered as Density left (R).

• A: Der Wert von (F)–(R) beträgt weniger als 0,02.
• B: Der Wert von (F)–(R) beträgt 0,02 oder mehr, bis weniger als 0,05.
• C: Der Wert von (F)–(R) beträgt 0,05 oder mehr, bis weniger als 0,10.
• D: Der Wert von (F)–(R) beträgt 0,10 oder mehr, bis weniger als 0,15.
• E: Der Wert von (F)–(R) beträgt 0,15 oder mehr.

The charging property of the magnetic toner was evaluated on the basis of the image density (F) before leaving, and the image density after leaving (R). The results of the evaluation are shown below.

• A: The value of (F) - (R) is less than 0.02.
• B: The value of (F) - (R) is 0.02 or more, to less than 0.05.
• C: The value of (F) - (R) is 0.05 or more, to less than 0.10.
• D: The value of (F) - (R) is 0.10 or more, to less than 0.15.
• E: The value of (F) - (R) is 0.15 or more.

The Results of the evaluation of the above are in Table 6.

Example 2

Median powder A-2 (magnetic toner particles) were obtained from finely pulverized product A2 in the same manner as in Example 1, except that the used multi-division gas flow classifier was changed from that in FIG 8th shown type. Here, the ratio of the weight of the finally obtained median powder (magnetic toner particles) to the total weight of the introduced powder material (that is, the classification yield) was 78%.

The Particle size of the median powder A-2 was as shown in Table 3.

Examples 3 to 6

Median powders A-3, A-4, A-5 and A-6 (magnetic toner particles) were obtained from finely pulverized products A3, A4, A5 and A6 in the same manner as in Example 1, except that Figs Conditions for pulverizing and classifying were changed to the in 4 shown system unit.

The Particle size of fine powdered products A3, A4, A5 and A6 and the median powder A-3, A-4, A-5 and A-6 were each as shown in Tables 2 and 3. Here also the system unit was operated under the conditions as shown in Table 5.

To 100 parts by weight of the median powder A-3, 1.0 parts by weight of the hydrophobic fine silica powder (BET specific surface area: 300 m ² / g); to 100 parts by weight of median powders A-4 and A-6, 0.6 parts by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g); and 100 parts by weight of median powder A-5, 1.2 parts by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) were each externally added using a Henschel stirrer to each magnetic toner (B), (C) To obtain (D) and (E).

Of the weight average particle diameter and circularity (measured with FPIA-1000) from each of the above magnetic toner was like shown in Table 4.

following an evaluation was carried out in the same manner as in Example 1 to those shown in Table 6 To get results.

Examples 7 to 18

Fine powdered products B to M and their corresponding median powder B-1 to M-1 were and the hydrophobic fine silica powder was externally added to obtain each magnetic toner (F) to (Q) in the same manner as in Example 1, except that the sulfur-containing copolymer was replaced with the types (b ) to (m) to form powder materials (B) to (M), respectively.

Of the weight average particle diameter and circularity (measured with FPIA-1000) from each of the above magnetic toner was like shown in Table 4.

in this connection were the particle size of the finely pulverized Products B to M and median powders B-1 to M-1 are each as in Tables 2 and 3 are shown. Also the system unit was operated under conditions as shown in Table 5.

following an evaluation was carried out in the same manner as in Example 1 to those shown in Table 6 To get results.

Comparative Example 1

The powder material (A) was finely pulverized and then classified using a system unit incorporated in 11 is shown. This in 13 The pulverizer shown was used as the collision air milling machine, as in 12 The device constructed in this way was used as a first classifier ( 52 in 11 ), and a device constructed as in 8th was used as a second classifier ( 57 in 11 ).

In 12 denotes reference number 401 a cylindrical main body housing; and 402 , a lower housing, at the lower part of a funnel 403 connected to unload coarse powder. Inside the main body 401 is a classifying chamber 404 formed, and is closed with a circular guide chamber 405 , attached to the upper part of this classifying chamber 404 and with a conical (umbrella-shaped) top cover 406 with a peak in the center.

Several roof tops 407 disposed in the peripheral direction are provided on a partition wall between the classifying chamber 404 and the leadership chamber 405 , The powder material and the air entering the guide chamber 405 be sent, swirling in a swirling manner from the openings of the individual roof tops 407 ,

An upper part of the leadership chamber 405 consists of a space formed between a conical shell cover 413 and a conical top cover 406 ,

The main body housing 401 is provided on the lower part with classifying roof attachments 409 , arranged in the direction of the circumference, and classifying air, which generates eddies, is from the outside over the classifying roof tops 409 into the classifying chamber 404 taken.

The classifying chamber 404 is at its bottom with a conical (umbrella-shaped) classifying plate 410 provided with an imaginary tip in its center, and a discharge opening 411 for coarse powder is formed along the periphery of the classifying plate 410 , Likewise, with the center of the classifying plate 410 a discharge trough 412 connected for fine powder. The gutter 412 is bent at its lower part in an L-shape, and the end of this bent part is positioned on the outside of the side wall of the lower-housing 402 , The gutter is further connected to a suction fan via a fine powder collecting device such as a cyclone or a dust collector. The suction fan causes a suction force in the classifying chamber 404 acts to create vortices necessary for classification by the action of the intake air entering the classifying chamber 404 flows over the roof tops 409 ,

In the present comparative example, a gas stream classifier constructed as described above is used as the first classifying means. The air containing the above powder material for producing the toner is introduced into the guide chamber 405 given from an air supply tube 408 , whereupon the air containing this powder material, on the individual roof tops 407 flows out of the leadership chamber 405 , and flows into the classifying chamber 404 while it is fluidized and dispersed in a uniform concentration.

The powder material that swirls into the classifying chamber 404 flows, is carried by the intake air, which flows through the classifying roof tops 409 provided at the lower part of the classifying chamber 404 to be swirled in an ascending manner, and separated into coarse powder and fine powder by centrifugal force by the action of the centrifugal force acting on the individual particles. The coarse powder that extends along the inner periphery of the classifying chamber 404 turns, is discharged from the discharge opening 411 for coarse powder, and is discharged from the classifier from the bottom hopper (coarse powder discharge hopper) 403 ,

The fine powder moving to the center along the top slope of the classifying chamber 404 , is discharged via the discharge chute 412 for fine powder.

The powder material was fed at a rate of 10.0 kg / hr by means of a first feeder 121 Table-type constant speed via an injection feeder 135 which was supplied via the supply tube 408 in the gas stream classifier, the in 12 and was classified by the effect of the centrifugal force acting on the individual particles. About the discharge hopper 403 for coarse powder, the coarse powder fractionated by the classification was shown in the collision air milling machine 13 , via its pulverizing material supply port 165 and then pulverized using compressed air of 0.588 MPa (6.0 kg / cm ² ) in pressure and 6.0 Nm 3 / min. Thereafter, the pulverized product was mixed with the toner pulverization material supplied into the material supply zone while the material was circulated to the gas flow classifier to repeatedly carry out pulverization. In the meantime, the fine powder obtained by classification was collected in a cyclone 131 accompanied by intake air drawn from an evacuation fan to obtain finely pulverized product N.

The this finely pulverized product N had a particle size distribution, that it had a weight average particle diameter of 6.7 μm, and 63.3% by number of particles of 4.0 μm or smaller in particle diameter and 11.1 volume percent particles of 10.1 μm or larger in particle diameter contained.

The thus obtained finely pulverized product N was introduced into the in 8th shown multi-division gas flow classifier, via a second power supply 124 constant speed to be classified into three fractions, coarse powder, median powder N-1 and fine powder, by using the Coanda effect via a vibrating feeder 125 and nozzles 148 and 149 at a speed of 13.0 kg / h. Upon introduction, suction force was used, which was derived from reduced pressure in the system by suction evacuation attributable to the collecting cyclones 129 . 130 and 131 that communicate with discharge openings 148 . 159 and 160 , Among them, obtained by classification, the coarse powder was collected by the collecting cyclone 129 , After that, it was introduced into the above collision air grinding machine 58 at a rate of 1.0 kg / h, and repeatedly introduced into the pulverization step.

The thus obtained by classification in the above classification step Median powder N-1 had a particle size distribution that it had a weight average particle diameter of 6.6 μm, and contained 23.3% by number of particles of 4.0 μm or smaller in particle diameter and 5.1% by volume of particles of 10.1 μm or larger in particle diameter.

in this connection was the ratio the weight of the median powder, that finally was obtained, the total weight of the imported material powder (the is called Classification yield) 69%.

To 100 parts by weight of this median powder N-1 was externally added 1.2 parts by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) using a Henschel stirrer to obtain comparative magnetic toner (a).

Of the Comparative Magenta Toner (a) had a weight average particle diameter of 6.5 μm. Measurement with FPIA-1000 in the comparative magnetoner (a) revealed that it contained 94.0% by weight particles with a circularity a from 0.900 or higher and 67.8% by weight of particles having a circularity a of 0.950 or higher.

The particle size distribution, the circularity distribution and the circle-corresponding diameter, measured with FPIA-1000, are shown graphically in FIG 17 to 19 ,

Evaluation was carried out in the same manner as in Example 1 to those shown in Table 6 To get results.

Comparative Example 2

The powder material (A) was finely pulverized and then classified using the in 11 shown system unit. The in 13 The conventional pulverizer shown was used as the collision air grinding machine. As a first classifying device, the gas flow classifier constructed as in FIG 12 As a result, when the powder material was fed at a rate of 8.0 kg / h, finely pulverized product O having a weight-average particle diameter of 5.9 μm was obtained and contained 72.3% by mass of particles of 4.0 μm or smaller in particle diameter and 8.0 volume percent of particles of 10.1 μm or larger in particle diameter.

Thereafter, the finely pulverized product thus obtained was introduced into the in 8th shown multi-division gas stream classifier to effect classification at a rate of 10.0 kg / h. Among those obtained by classification, the coarse powder was collected by the collecting cyclone 129 , After that, it was introduced into the above collision air grinding machine 58 at a rate of 1.0 kg / h, and repeatedly introduced into the pulverization step.

The thus obtained by classification in the above classification step Median powder O-1 had a particle size distribution that it had a weight average particle diameter of 6.0 μm and contained 33.8 number percent particles of 4.0 μm or smaller in particle diameter and 4.1% by volume particles of 10.1 μm or larger in particle diameter.

in this connection was the ratio the weight of the median powder, that finally to the total weight of the powder material that was introduced (i.e., classification yield) 63%.

To 100 parts by weight of this median powder O-1 was externally added 1.2 parts by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) using a Henschel stirrer to obtain comparative magnetic toner (b).

The Results of measurement with FPIA-1000 in comparison magnetoner (b) were as shown in Table 4.

evaluation was carried out in the same manner as in Example 1, to the results shown in Table 6 to obtain.

Comparative Example 3

powder material (P) was obtained in the same manner as in Example 1, with with the exception that the sulfur-containing copolymer (a) exchanged was used against a monoazo metal complex (control agent negative Charge). This powder material (P) was finely pulverized and thereafter classified using the same system unit as the one in Example 1. The resulting finely pulverized product P and median powder P-1 had a particle size as in Tables 2 and 3 are shown. Also the system was operated under Conditions as shown in Table 5. Here was the ratio of Weight of the finally obtained median powder to the total weight of the powder material, that introduced was (that is Classification yield) 81%.

To 100 parts by weight of this median powder P-1 was externally added 1.2 parts by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) using a Henschel stirrer to obtain comparative magnetic toner (c).

The Results of measurement with FPIA-1000 in comparison magnetoner (c) were as shown in Table 4.

evaluation was carried out in the same manner as in Example 1, to the results shown in Table 6 to obtain.

Comparative Example 4

Finely pulverized product Q and median powder Q-1 were obtained in the same manner as in Example 1 with the exception that the powder material (P) prepared in Comparative Example 3 was used. The obtained finely pulverized product Q and median powder Q-1 had a particle size as shown in Tables 2 and 3. Here, the system was operated under conditions as shown in Table 5. Also, the ratio of the weight of the median powder finally obtained to the total weight of the powder material that was introduced (that is, the classification yield) was 83%.

To 100 parts by weight of this median powder Q-1 was externally added 1.2 parts by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) using a Henschel stirrer to obtain comparative magnetic toner (d).

The Results of measurement with FPIA-1000 in comparison magnetoner (d) were as shown in Table 4.

evaluation was carried out in the same manner as in Example 1, to the results shown in Table 6 to obtain.

Examples 19 and 20

Using the powder material (A), median powders A-7 and A-8 (classified products) were prepared in the same manner as in Example 1 except that the conditions for pulverization and classification using the system unit, in 4 shown, changed. Finely pulverized products A7 and A8 and median powders A-7 and A-8 obtained had a particle size as shown in Tables 2 and 3. Here, the system was operated under conditions as shown in Table 5.

To 100 parts by weight of median powder A-7, 1.5 parts by weight of hydrophobic fine silica powder (BET specific surface area: 180 m ² / g); and 100 parts by weight of the median powder A-8, 1.0 part by weight of hydrophobic fine silica powder (BET specific surface area: 180 m ² / g) were externally added using a Henschel stirrer to mix each magnetic toner (R) and (S ) to obtain.

Of the weight average particle diameter and circularity (measured with FPIA-1000) of each of the magnetic toners (R) and (S) were as shown in Table 4.

evaluation was carried out in the same manner as in Example 1, to the results shown in Table 6 to obtain.

Comparative Example 5

Using the powder material (A), median powder R-1 (classified products) was prepared in the same manner as in Comparative Example 1 except that the conditions for pulverization and classification using the system unit shown in FIG 11 , have been changed. Finely pulverized product R1 and median powder R-1, which were obtained, had a particle size as shown in Tables 2 and 3. Here, the system was operated under conditions as shown in Table 5.

To 100 parts by weight of this median powder R-1 was externally added 1.5 parts by weight of hydrophobic fine silica powder (BET specific surface area: 180 m ² / g) using a Henschel stirrer to obtain comparative magnetic toner (e).

Of the weight average particle diameter and circularity (measured with FPIA-1000) of comparative magnetic toner (e) was as shown in Table 4.

evaluation was carried out in the same manner as in Example 1, to the results shown in Table 6 to obtain.

Production Example 1 of inorganic fine powder

(Fine Strontium Titanate Powder)

Using a ball mill, 600 g of strontium carbonate and 320 g of titanium oxide were mixed in a wet process for 8 hours, followed by filtration and drying. The resulting mixture was molded under a pressure of 0.49 MPa (5 kg / cm ² ), followed by calcining at 1100 ° C for 8 hours. The The obtained calcined product was mechanically pulverized to obtain fine strontium titanate powder (M-1) having a weight-average particle diameter of 2.0 μm.

Preparation Examples 2 and 3 for inorganic fine powder

(Fine strontium titanate powder)

The calcined in the same manner as in Production Example 1 Product was pulverized and classified under different conditions, to obtain fine strontium titanate powders with a weight average Particle diameter of 4.8 microns (M-2) and a weight average particle diameter of 0.3 μm (M-3).

Production Example 4 for inorganic fine powder

(Fine calcium titanate powder)

Using a ball mill, 505 g of calcium carbonate and 400 g of titanium oxide were mixed in a wet process for 8 hours, followed by filtration and drying. The resulting mixture was molded under a pressure of 0.49 MPa (5 kg / cm ² ) followed by calcining at 1100 ° C for 8 hours. The obtained calcined product was mechanically pulverized to obtain fine calcium titanate powder (M-4) having a weight-average particle diameter of 1.8 μm.

Example 21

To 100 parts by weight of the median powder A-1 (toner particles) obtained in Example 1 were added 1.0 part by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) and 4.0 parts by weight of fine strontium titanate powder (M-1 ) externally to produce magnetic toner (T). Its various properties are shown in Table 7.

Example 22

To 100 parts by weight of the median powder A-1 (toner particles) obtained in Example 1, 1.0 part by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) and 4.0 parts by weight of the fine strontium titanate powder (M ² ) were used. 2) externally added to produce magnetic toner (U). Its various properties are shown in Table 7.

Example 23

To 100 parts by weight of the median powder A-1 (toner particles) obtained in Example 1 were added 1.0 part by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) and 4.0 parts by weight of fine strontium titanate powder (M-3 ) externally to produce magnetic toner (V). Its various properties are shown in Table 7.

Example 24

To 100 parts by weight of the median powder A-1 (toner particles) obtained in Example 1 were added 1.0 part by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) and 4.0 parts by weight of the fine calcium titanate powder (M ² ). 4) added externally to produce magnetic toner (W). Its various properties are shown in Table 7.

Comparative Example 6

To 100 parts by weight of the median powder N-1 (toner particles) obtained in Comparative Example 1, 1.0 part by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) and 4.0 parts by weight of fine strontium titanate powder (M-1 ) is externally added to make comparison magneto toner (f). Its various properties are shown in Table 7.

Comparative Example 7

To 100 parts by weight of the median powder P-1 (toner particles) obtained in Comparative Example 3, w externally added to 1.0 part by weight of hydrophobic fine silica powder (BET specific surface area: 300 m ² / g) and 4.0 parts by weight of fine strontium titanate powder (M-1) to prepare comparative magnetic toner (g). Its various properties are shown in Table 7.

Under Using the magnetic toners (T), (U), (V) and (W) and the comparison magneto toner (f) and (g), evaluation was carried out in terms of transfer efficiency (%), Fogging and charging feature. Evaluation was also performed in the following way, as to whether or not faulty Cleaning, drum wear and smeared images occurred. The Results of the evaluation are shown in Table 8.

- faulty Cleaning and drum wear -

Under Using a modified copying machine NP6085, manufactured by CANON INC., Modified so that all development, drum, optical and paper feeding systems were set to increase the copying speed by 20%, Images were reproduced on 100,000 sheets in a normal temperature-low humidity environment (23 ° C / 5% RH), in this regard to carry out an evaluation whether or not faulty cleaning occurred, and in relation to the depth of drum wear. This was the cleaning blade brought into contact with the drum surface at a total pressure of 5.88 N (600 g).

Evaluation of cleaning:

• A: no faulty cleaning occurs.
• B: faulty cleaning is easily recognizable on the white background.
• C: faulty cleaning is clearly visible in pictures.

Evaluation of drum wear:

• A: Wear is at a depth of less as 10.0 Å.
• B: Wear is at a depth of 10.0 Å to less as 25.0 Å.
• C: Wear is at a depth of 25.0 Å to less as 50.0 Å.
• D: Wear is at a depth of 50.0 Å to less as 150.0 Å.
• E: Wear is at a depth of 150.0 Å or more.

- smeared Images -

Under Using a modified copying machine NP6085, manufactured by CANON INC., Modified so that all development, drum, optical and paper feeding systems were set to increase the copying speed by 20%, Images were reproduced on 500,000 leaves in a high temperature, high humidity environment (32.5 ° C / 85% RH), to check if or if smeared images did not occur. This was the purifying Blade brought into contact with the drum surface at a total pressure of 5.49 N (560 g).

• A: Empty pictures have an area of 0th
• B: Empty images have an area of less than 1 cm ² .
• C: Empty images have an area of 1 cm ² to less than 5 cm ² .
• D: Empty images have an area of 5 cm ² to less than 10 cm ² .
• E: Empty pictures have an area of 10 cm ² or more.

Claims (36)

Toner having toner particles containing at least (i) a binder resin, (ii) a dye, and (iii) a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, wherein; the toner has a weight average particle diameter of 5 μm to 12 μm; and the toner among its particles, which are 3 μm or larger in diameter, has at least 90% by weight of particles having a circularity a of 0.900 or higher, as determined according to the following expression: Circularity a = L 0 / L (1) where L _{0 represents} the circumferential length of a circle having the same projected area as a particle image, and L represents the circumferential length of the particle image; and where; a) the relationship between the division rate Z and the weight-average toner particle diameter X satisfies the following expression (2): Division rate Z ≤ 5.3 × X (2) provided that the division rate Z is represented by the following expression (3): Z = (1-B / A) × 100 (3) wherein A is the particle concentration of the total measured particles as measured by a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and B is the particle concentration of the measured particles of 3 μm or larger in the circle-corresponding diameter; and in the particles of 3 μm or larger in diameter of the toner, and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher and the weight-average toner particle diameter X satisfies the following expression (4): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.51 × X -0.645 (4) provided that the weight average toner particle diameter X is from 5.0 μm to 12 μm; or b) the relationship between the division rate Z and the weight average toner particle diameter X satisfies the following expression (5): Division rate Z> 5.3 × X (5); and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of the particles having a circularity a of 0.950 or higher and the weight-average toner particle diameter X dem the following expression (6) satisfies: Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.37 × X -0.545 (6) provided that the weight average toner particle diameter X is from 5.0 to 12 μm. The toner according to claim 1, wherein the sulfur-containing Compound is a polymer having a sulfonic acid group. The toner according to claim 1, wherein the sulfur-containing Compound is a copolymer having a sulfonic acid group. The toner according to claim 1, wherein the sulfur-containing Compound is a copolymer of an acrylamide sulfonic acid monomer with a vinyl monomer. The toner according to claim 1, wherein the sulfur-containing compound is a copolymer of 2-acryla is mid-2-methylpropanesulfonic acid with a vinyl monomer. The toner according to claim 1, wherein the sulfur-containing Compound a copolymer of a styrene monomer and an acrylic monomer with a sulfonic acid-containing Acrylamide monomer is. The toner according to claim 1, wherein the sulfur-containing Connection is a regulator with negative charge. The toner according to claim 1, wherein the sulfur-containing Compound a weight average molecular weight Mw from 2000 to 200 000 has. The toner according to claim 1, wherein the sulfur-containing Compound a weight average molecular weight Mw of 17000 to 100 000 has. The toner according to claim 1, wherein the sulfur-containing Compound has a weight average molecular weight Mw of 27,000 to Has 50,000. The toner according to claim 1, wherein the sulfur-containing Compound a glass transition temperature Tg of 30 ° C up to 120 ° C Has. The toner according to claim 1, wherein the sulfur-containing Compound a glass transition temperature Tg from 50 ° C up to 100 ° C Has. The toner according to claim 1, wherein the sulfur-containing Compound a glass transition temperature Tg from 70 ° C up to 95 ° C Has. The toner according to claim 1, wherein the sulfur-containing Compound a copolymer of a styrene monomer and an acrylic monomer with 2-acrylamide-2-methylpropanesulfonic acid. The toner according to claim 1, wherein the toner particles are obtained are obtained by melt-kneading a mixture containing at least a binder resin, a dye and a sulfur-containing compound, cooling down the resulting kneaded product, crushing the resulting cooled product, and pulverizing the resulting crushed product by means of a mechanical grinding machine. The toner according to claim 15, wherein the sulfur-containing end Compound was pulverized before the step of melt-kneading is to have a mean particle diameter of 300 μm or less to own. The toner according to claim 15, wherein the sulfur-containing end Compound was pulverized before the step of melt-kneading is to have a mean particle diameter of 150 μm or less to own. The toner of claim 15, wherein the crushed product is pulverized by means of the mechanical grinding machine, and that resulting pulverized product classified by means of an air classifier is to get the toner particles. The toner according to claim 18, wherein the toner particles are formed from a median powder obtained by melt-kneading the mixture containing at least a binder resin, a dye and a sulfur-containing compound, cooling the obtained kneaded product, and then crushing the same cooled product by a crushing device; Introducing the resulting crushed product as a powder material into a first constant speed feeder; Introducing the powder material in a fixed quantity into a mechanical grinding machine from the first constant speed feeder via a powder material inlet of the mechanical grinding machine; wherein the mechanical grinding machine has at least one rotor comprising a rotator mounted on the central rotating shaft and a stator located around the rotor so as to maintain a certain space between itself and the rotor surface, and thus constructed in that a circular space formed by keeping the space is airtight; Rotating the rotor of the mechanical grinding machine at a high speed to finely pulverize the powder material to form a finely pulverized product having a weight-average particle diameter of 5 to 12 μm, and 70 number percent or less particles of 4.0 μm or less in the Particle diameter and 25% by volume or less of particles of 10.1 μm or larger in particle diameter; Discharging the finely pulverized product from a powder material discharge port of the mechanical grinding machine and introducing the finely pulverized product into a second constant-speed food processor; Introducing the finely pulverized product in a fixed quantity into a multi-section gas stream classifier classifying the powder material by using the intersecting gas streams and the Coanda effect; Classifying the finely pulverized powder in the multi-section gas stream classifier into at least fine powder, median powder and coarse powder to obtain the median powder; and mixing the classified coarse powder with the powder material and introducing it into the mechanical milling machine to perform pulverization and classification to obtain the median powder. The toner according to claim 1, which contains 40% by number or less particles of 4.0 microns or smaller in particle diameter and 25 volume percent or less particles of 10.1 μm or larger in particle diameter. The toner according to claim 1, which has a circularity standard deviation SD from 0.030 to 0.045. The toner according to claim 1, wherein the sulfur-containing Compound an acid value from 3 mg · KOH / g to 80 mg · KOH / g Has. The toner according to claim 1, wherein the sulfur-containing Compound an acid value from 5 mg · KOH / g to 40 mg · KOH / g. The toner according to claim 1, wherein the sulfur-containing Compound an acid value of 10 mg · KOH / g to 30 mg · KOH / g Has. The toner according to claim 1, wherein the sulfur-containing Connection a fleeting Proportion of 0.01 to 2.0%. The toner according to claim 1, wherein the sulfur-containing Connection a fleeting Proportion of 0.01 to 1.0%. The toner according to claim 1, wherein the sulfur-containing Compound in an amount of 0.01 part by weight to 15 parts by weight based on 100 parts by weight of the binder resin is included. The toner according to claim 1, wherein the sulfur-containing Compound is contained in an amount of 0.10 parts by weight to 10 parts by weight based on 100 parts by weight of the binder resin. An image forming method comprising; Generating an electrostatic latent image on an electrostatic image bearing member; Developing the electrostatic latent image with a toner held in a developing device to form a toner image; Transferring the toner image formed in this manner to a transfer medium via, or not via, an intermediate transfer member; Fixing the toner image carried on the transfer medium to the transfer medium by a heat and pressure fixing means; in which; the toner comprises toner particles containing at least (i) a binder resin, (ii) a dye, and (iii) a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, wherein; the toner has a weight average particle diameter of 5 μm to 12 μm; and the toner in its particles of 3 μm or larger in diameter has at least 90% by weight of particles having a circularity a of 0.900 or higher as determined according to the following expression (1): Circularity a = L 0 / L (1) where L ₀ represents the circumferential length of a circle having the same projected area as a particle image, and L represents the circumferential length of the particle image; and where; a) the relationship between the division rate Z and the weight average toner particle diameter X satisfies the following expression (2): Division rate Z ≤ 5.3 × X (2) provided that the division rate Z is represented by the following expression (3): Z = (1-B / A) × 100 (3) wherein A is the particle concentration of the total measured particles as measured by a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and B is the particle concentration of the measured particles of 3 μm or larger in the circle-corresponding diameter; and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher and the weighted average Toner particle diameter X satisfies the following expression (4): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.51 × X -0.645 (4) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm; or b) the relationship between the division rate Z and the weight average toner particle diameter X satisfies the following expression (5): Division rate Z> 5.3 × X (5); and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher and the weighted average Toner particle diameter X satisfies the following expression (6): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.37 × X -0.545 (6) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm. The method of claim 29, wherein; the the Electrostatic image bearing element electrostatically charged is powered by a contact charging device to which a bias has been created; the thus charged the electrostatic Image bearing element is exposed to a digital latent To create an image; the digital latent image with the in the Developing device worn toner is developed to the toner image to create; and the toner image is transferred to the transfer medium via, or no over, the intermediate transmission element by a contact transfer device, to which a bias voltage has been applied. The method of claim 29, wherein; the toner a magnetic toner is magnetic toner particles that contain a magnetic material; and the developing device has a developing sleeve, provided internally with a magnetic field generating means and an elastic blade for generating a magnetic toner layer on the developing sleeve. The method of claim 29, wherein the toner is the Toner according to a the claims 2 to 28 is. A process cartridge having an electrostatic image-bearing member and developing means for developing an electrosta generated on the electrostatic image bearing member latent latent image, with a toner; wherein the electrostatic image bearing member and the developing means are supported in one unit to form the process cartridge, and the process cartridge is detachably mountable to the main body of an image forming apparatus; in which; the toner comprises toner particles containing at least (i) a binder resin, (ii) a dye, and (iii) a sulfur-containing compound selected from the group consisting of a sulfur-containing polymer and a sulfur-containing copolymer, wherein; the toner has a weight average particle diameter of 5 μm to 12 μm; and the toner in its particles of 3 μm or larger in diameter has at least 90% by weight of particles having a circularity α of 0.900 or higher, as determined according to the following expression (1): Circularity a = L 0 / L (1) where L ₀ represents the circumferential length of a circle having the same projected area as a particle image, and L represents the circumferential length of the particle image; and where; a) the relationship between the division rate Z and the weight-average toner particle diameter X satisfies the following expression (2): Division rate Z ≤ 5.3 × X (2) provided that the division rate Z is represented by the following expression (3): Z = (1-B / A) × 100 (3) wherein A is the particle concentration of the total measured particles as measured by a flow type particle image analyzer FPIA-1000 manufactured by Toa Iyou Denshi KK, and B is the particle concentration of the measured particles of 3 μm or larger in the circle-corresponding diameter; and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher and the weighted average Toner particle diameter X satisfies the following expression (4): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5.51 × X -0.645 (4) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm; or b) the relationship between the division rate Z and the weight-average toner particle diameter X satisfies the following expression (5): Division rate Z> 5.3 × X (5); and in the particles of 3 μm or larger in diameter of the toner and in the number-based circularity distribution of the circularity a, the relationship between the number-based cumulative value Y of particles having a circularity a of 0.950 or higher and the weighted average Toner particle diameter X satisfies the following expression (6): Number-based cumulative value Y of particles having a circularity a of 0.950 or higher ≥ e 5:37 × X -0.545 (6) provided that the weight average toner particle diameter X is from 5.0 μm to 12.0 μm. The process cartridge of claim 33, wherein the electrostatic image bearing element a photosensitive drum is. The process cartridge of claim 33, further comprising a contact charging device. A process cartridge according to claim 33, wherein the toner is the toner according to any one of claims 2 to 28 is.